Working fluid for heat cycle, composition for heat cycle system, and heat cycle system

ABSTRACT

An object of the present invention is to provide, as a working fluid to be used for a heat cycle system, a working fluid for heat cycle that has cycle performance replaceable with that of R410A, and at the same time, has a small burden on an apparatus, low flammability, suppressed self-decomposition, and less effect on global warming, and therefore, is usable stably even if leaked, a composition for heat cycle system containing the same, and a heat cycle system using the composition. The working fluid for heat cycle contains trifluoroethylene, difluoromethane, and at least one selected from 1,1-difluoroethane, fluoroethane, propane, propylene, carbon dioxide, 2,3,3,3-tetrafluoropropene, and (E)-1,3,3,3-tetrafluoropropene at mass ratios satisfying predetermined expressions and at a ratio of the total content to be 90 to 100 mass % relative to the total amount of the working fluid and has a temperature glide of 10° C. or less.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of prior International ApplicationNo. PCT/JP2017/031946 filed on Sep. 5, 2017 which is based upon andclaims the benefit of priority from Japanese Patent Application No.2016-174940 filed on Sep. 7, 2016; the entire contents of all of whichare incorporated herein by reference.

FIELD

The present invention relates to a working fluid for heat cycle, acomposition for heat cycle system containing the same, and a heat cyclesystem using the composition.

BACKGROUND

Conventionally, as working fluids for a heat cycle system such as arefrigerant for a refrigerator, a refrigerant for an air-conditioningapparatus, a working fluid for a power generation system (such as anexhaust heat recovery power generation), a working fluid for a latentheat transport apparatus (such as a heat pipe), and a secondary coolingmedium, chlorofluorocarbon (CFC) such as chlorotrifluoromethane anddichlorodifluoromethane and hydrochlorofluorocarbon (HCFC) such aschlorodifluoromethane have been used. However, effects of CFC and HCFCon the ozone layer in the stratosphere have been pointed out, and theyare subjected to regulation at present.

Under such circumstances, as a working fluid for heat cycle to be usedfor a heat cycle system, hydrofluorocarbon (HFC) having less effect onthe ozone layer, such as difluoromethane (HFC-32), tetrafluoroethane,and pentafluoroethane (HFC-125), has been used in place of CFC and HCFC.For example, R410A (a pseudoazeotropic mixture refrigerant of HFC-32 andHFC-125 at a mass ratio of 1:1) or the like is a refrigerant that hasbeen widely used conventionally. However, it has been pointed out thatHFC may cause global warming.

R410A has been widely used for normal air-conditioning apparatuses orthe like what is called a packaged air-conditioner and a roomair-conditioner due to its high refrigerating capacity. However, R410Ahas a global warming potential (GWP) as high as 2088, and therefore, thedevelopment of a low GWP working fluid has been required. In this case,there has been required development of a working fluid on the premisethat an apparatus that has been used is continuously used as it is justby replacing R410A.

In recent years, expectations are concentrated on hydrofluoroolefin(HFO), that is, HFC having a carbon-carbon double bond, which is aworking fluid having less effect on the ozone layer and less effect onglobal warming because the carbon-carbon double bond is likely to bedecomposed by OH radicals in the air. In this description, saturated HFCis called HFC and discriminated from HFO unless otherwise noted.Further, HFC is sometimes clearly described as saturatedhydrofluorocarbon.

As a working fluid using HFO, for example, there has been disclosed atechnique relating to a working fluid using trifluoroethylene (HFO-1123)having the above-described properties and capable of obtaining excellentcycle performance in Patent Reference 1 (International Publication No.2012/157764). In Patent Reference 1, there has further been attempted toenable a working fluid in which various HFC and HFO are combined withHFO-1123 in order to increase nonflammability, cycle performance, and soon of the working fluid.

Here, HFO-1123 sometimes causes what is called a self-decompositionreaction when there is an ignition source at higher temperature or underhigh pressure. Therefore, there has been attempted to obtain a workingfluid in which the working fluid using HFO-1123 is combined with othercomponents to suppress the self-decomposition reaction of HFO-1123.There has been described in, for example, Patent Reference 2 (JapanesePatent No. 5783341) that a working fluid having high durability in whichHFO-1123, HFC-32, and 2,3,3,3-tetrafluoropropene (HFO-1234yf) are mixedat a predetermined ratio to thereby suppress the self-decompositionreaction of HFO-1123 is obtained.

However, as the working fluid to be used for the heat cycle system, asafer working fluid that is lower in environmental burden and higher inperformance has been required, and a working fluid for heat cycle inwhich the self-decomposition reaction of HFO-1123 is suppressed underconditions stricter than those described in Patent Reference 2, forexample, has been required.

SUMMARY OF THE INVENTION

An object of the present invention is to provide, as a working fluid tobe used for a heat cycle system, a working fluid for heat cycle that hascycle performance replaceable with that of R410A, and at the same time,has a small burden on an apparatus, low flammability, suppressedself-decomposition, and less effect on global warming, and therefore, isusable stably even if leaked, a composition for heat cycle systemcontaining the same, and a heat cycle system using the composition.

The present invention provides a working fluid for heat cycle, acomposition for heat cycle system, and a heat cycle system that have thefollowing configurations.

A working fluid for heat cycle according to a first aspect of thepresent invention is a working fluid for heat cycle containingtrifluoroethylene and difluoromethane, the working fluid for heat cyclefurther containing: at least one compound selected from the groupconsisting of 1,1-difluoroethane, fluoroethane, propane, propylene,carbon dioxide, 2,3,3,3-tetrafluoropropene, and(E)-1,3,3,3-tetrafluoropropene, in which

the total content ratio of trifluoroethylene, difluoromethane,1,1-difluoroethane, fluoroethane, propane, propylene, carbon dioxide,2,3,3,3-tetrafluoropropene, and (E)-1,3,3,3-tetrafluoropropene relativeto the total amount of the working fluid for heat cycle is 90 to 100mass %,

content ratios by mass of the respective compounds satisfy allExpression A to Expression E below when the total content oftrifluoroethylene, difluoromethane, 1,1-difluoroethane, fluoroethane,propane, propylene, carbon dioxide, 2,3,3,3-tetrafluoropropene, and(E)-1,3,3,3-tetrafluoropropene contained in the working fluid for heatcycle is set to 1, and

a temperature glide is 10° C. or less when operating a standardrefrigeration cycle system under a temperature condition (T) that in thecase of the working fluid for heat cycle being a zeotropic mixture, anaverage temperature of an evaporation start temperature and anevaporation completion temperature is 0° C., in the case of the workingfluid for heat cycle being an azeotropic mixture, an evaporationtemperature is 0° C., in the case of the working fluid for heat cyclebeing a zeotropic mixture, an average temperature of a condensationstart temperature and a condensation completion temperature is 40° C.,in the case of the working fluid for heat cycle being an azeotropicmixture, a condensation temperature is 40° C. a degree of supercooling(SC) is 5° C., and a degree of superheating (SH) is 5° C.,

0<−1.000×[HFO-1123]+1.179×[R32]+1.316×[1234yf]+1.316×[1234ze(E)]+3.831×[CO2]+2.632×[R152a]+2.390×[R161]+6.262×[propane]+2.237×[propylene],  ExpressionA;

10>3.426×[HFO-1123]+5.673×[R32]+2.193×[1234yf]−0.596×[1234ze(E)]−0.768×[CO2]+29.897×[R152a]+64.400×[R161]+118.965×[propane]+94.943×[propylene],  ExpressionB;

1.78>1.293×[HFO-1123]+1.029×[R32]+0.369×[1234yf]+0.354×[1234ze(E)]+3.807×[CO2]+0.229×[R152a]+0.406×[R161]+0.568×[propane]+0.719×[propylene],  ExpressionC;

0.91<1.214×[HFO-1123]+1.133×[R32]+0.402×[1234yf]+0.346×[1234ze(E)]+3.359×[CO2]+0.323×[R152a]+0.548×[R161]+0.588×[propane]+0.725×[propylene],and  Expression D;

160>0.3×[HFO-1123]+675×[R32]+4×[1234yf]+6×[1234ze(E)]+1×[CO2]+124×[R152a]+12×[R161]+3.3×[propane]+1.8×[propylene],  ExpressionE;

where in Expression A to Expression E, [HFO-1123] represents the contentratio by mass of trifluoroethylene, [R32] represents the content ratioby mass of difluoromethane, [R152a] represents the content ratio by massof 1,1-difluoroethane, [R161] represents the content ratio by mass offluoroethane, [propane] represents the content ratio by mass of propane,[propylene] represents the content ratio by mass of propylene, [CO2]represents the content ratio by mass of carbon dioxide, [1234yf]represents the content ratio by mass of 2,3,3,3-tetrafluoropropene, and[1234ze(E)] represents the content ratio by mass of(E)-1,3,3,3-tetrafluoropropene respectively when the total content oftrifluoroethylene, difluoromethane, 1,1-difluoroethane, fluoroethane,propane, propylene, carbon dioxide, 2,3,3,3-tetrafluoropropene, and(E)-1,3,3,3-tetrafluoropropene is set to 1.

A working fluid for heat cycle according to a second aspect of thepresent invention is a working fluid for heat cycle containingtrifluoroethylene and difluoromethane, the working fluid for heat cyclefurther containing: at least one compound selected from the groupconsisting of 1,1-difluoroethane, fluoroethane, propane, propylene,carbon dioxide, 2,3,3,3-tetrafluoropropene, and(E)-1,3,3,3-tetrafluoropropene, in which

the total content ratio of trifluoroethylene, difluoromethane,1,1-difluoroethane, fluoroethane, propane, propylene, carbon dioxide,2,3,3,3-tetrafluoropropene, and (E)-1,3,3,3-tetrafluoropropene relativeto the total amount of the working fluid for heat cycle is 90 to 100mass %,

content ratios by mass of the respective compounds satisfy allExpression A2 below and Expression B, Expression C, Expression D, andExpression E above when the total content of trifluoroethylene,difluoromethane, 1,1-difluoroethane, fluoroethane, propane, propylene,carbon dioxide, 2,3,3,3-tetrafluoropropene, and(E)-1,3,3,3-tetrafluoropropene contained in the working fluid for heatcycle is set to 1, and a temperature glide is 10° C. or less whenoperating a standard refrigeration cycle system under a temperaturecondition (T) that in the case of the working fluid for heat cycle beinga zeotropic mixture, an average temperature of an evaporation starttemperature and an evaporation completion temperature is 0° C., in thecase of the working fluid for heat cycle being an azeotropic mixture, anevaporation temperature is 0° C., in the case of the working fluid forheat cycle being a zeotropic mixture, an average temperature of acondensation start temperature and a condensation completion temperatureis 40° C., in the case of the working fluid for heat cycle being anazeotropic mixture, a condensation temperature is 40° C., a degree ofsupercooling (SC) is 5° C., and a degree of superheating (SH) is 5° C.,

0<−1.000×[HFO-1123]+1.033×[R32]+0.896×[1234yf]+0.896×[1234ze(E)]+2.891×[CO2]+1.955×[R152a]+1.410×[R161]+3.737×[propane]+1.520×[propylene],  ExpressionA2;

where in Expression A2, [HFO-1123], [R32], [R152a], [R161], [propane],[propylene], [CO2], [1234yf], and [1234ze(E)] mean the same as those in[1] above.

The present invention provides a composition for heat cycle systemcontaining the working fluid for heat cycle according to the firstaspect or the second aspect of the present invention and a lubricatingoil. The present invention provides a heat cycle system using thecomposition for heat cycle system of the present invention.

According to the present invention, as a working fluid to be used for aheat cycle system, it is possible to obtain a working fluid that hascycle performance replaceable with that of R410A and at the same time,has a small burden on an apparatus. Further, it is possible to provide aworking fluid for heat cycle that has low flammability, suppressedself-decomposition, and less effect on global warming, and therefore, isusable stably even if leaked and a composition for heat cycle systemcontaining the same. The heat cycle system of the present invention is aheat cycle system that does not require special processes on anapparatus and to which the composition for heat cycle system replaceablewith R410A and having less effect on global warming is applied.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic configuration diagram illustrating one example ofa standard refrigeration cycle system that evaluates a heat cycle systemof the present invention.

FIG. 2 is a cycle chart illustrating change of state of a working fluidin the refrigeration cycle system in FIG. 1 on a pressure-enthalpy linediagram.

FIG. 3 is a view illustrating a composition range of one embodiment of aworking fluid for heat cycle of the present invention in a triangularcoordinate chart of a composition (mass %) of HFO-1123, carbon dioxide,and R161 when R32 in a mixture composed of HFO-1123, R32, carbondioxide, and R161, where [R161] may be 0 mass %, is set to apredetermined amount.

MODE FOR CARRYING OUT THE INVENTION

Hereinafter, there will be explained embodiments of the presentinvention. Incidentally, in this description, for halogenatedhydrocarbons, an abbreviated name of a compound is described betweenparentheses after the compound name, and the abbreviated name is used inplace of the compound name as needed in this description. Further, (E)and (Z) added to the name or abbreviation of a compound having ageometric isomer represent an E-isomer (trans-isomer) and a Z-isomer(cis-isomer) respectively. The name or abbreviation of the compoundwithout the notation of the E-isomer or the Z-isomer means a genericname including the E-isomer, the Z-isomer, or a mixture of the E-isomerand the Z-isomer. In this description, “to” indicating the numericalvalue range includes upper and lower limits.

In this description, [HFO-1123] represents the content ratio by mass oftrifluoroethylene, [R32] represents the content ratio by mass ofdifluoromethane, [R152a] represents the content ratio by mass of1,1-difluoroethane, [R161] represents the content ratio by mass offluoroethane, [propane] represents the content ratio by mass of propane,[propylene] represents the content ratio by mass of propylene, [CO2]represents the content ratio by mass of carbon dioxide, [1234yf]represents the content ratio by mass of 2,3,3,3-tetrafluoropropene, and[1234ze(E)] represents the content ratio by mass of(E)-1,3,3,3-tetrafluoropropene respectively when the total content oftrifluoroethylene, difluoromethane, 1,1-difluoroethane, fluoroethane,propane, propylene, carbon dioxide, 2,3,3,3-tetrafluoropropene, and(E)-1,3,3,3-tetrafluoropropene is set to 1 unless otherwise noted.

Of the present invention, a working fluid for heat cycle in a firstaspect is also referred to as a first working fluid and a working fluidfor heat cycle in a second aspect is also referred to as a secondworking fluid. Further, in this description, the case of a simpleworking fluid indicates both the first working fluid and the secondworking fluid.

The first working fluid and the second working fluid each contain

trifluoroethylene (HFO-1123),

difluoromethane (HFC-32 or R-32, or to be also referred to as R32), and

at least one selected from 1,1-difluoroethane (HFC-152a or R-152a, or tobe also referred to as R152a), fluoroethane (HFC-161 or R-161, or to bealso referred to as R161), propane, propylene, carbon dioxide,2,3,3,3-tetrafluoropropene (HFO-1234yf, or to be also referred to as1234yf), and (E)-1,3,3,3-tetrafluoropropene (HFO-1234ze(E), or to bealso referred to as 1234ze(E))

at the following content ratios.

The total content ratio of HFO-1123, R32, R152a, R161, propane,propylene, carbon dioxide, 1234yf, and 1234ze(E) in the working fluid is90 to 100 mass % relative to the total amount of the working fluid. Thecontent ratio of each compound in the working fluid is the content ratioby mass of each compound when the total content of all these compoundsin the working fluid is set to 1, and is the ratio satisfying allExpression A, Expression B, Expression C, Expression D, and Expression Edescribed above in the first working fluid. The content ratio of eachcompound in the working fluid is the ratio satisfying all Expression A2,Expression B, Expression C, Expression D, and Expression E describedabove in the second working fluid.

Further, the working fluid of the present invention has a temperatureglide of 10° C. or less when operating a standard refrigeration cyclesystem under the following temperature condition (T).

[Temperature Condition (T)]

The average temperature of an evaporation start temperature and anevaporation completion temperature in the case of the working fluidbeing a zeotropic mixture, and the evaporation start temperature in thecase of the working fluid being an azeotropic mixture are 0° C.The average temperature of a condensation start temperature and acondensation completion temperature in the case of the working fluidbeing a zeotropic mixture, and the condensation temperature in the caseof the working fluid being an azeotropic mixture are 40° C.Degree of supercooling (SC) is 5° C.Degree of superheating (SH) is 5° C.

Expressions A to Expression E described above in the first working fluidare relational expressions of the content ratios by mass of theabove-described compounds intended for satisfying the followingproperties of (A) to (E) corresponding to Expressions A to Expression Erespectively in a working fluid composed of only HFO-1123, R32, and atleast one selected from R152a, R161, propane, propylene, carbon dioxide,1234yf, and 1234ze(E). Hereinafter, the working fluid having acomposition composed of only HFO-1123, R32, and at least one selectedfrom R152a, R161, propane, propylene, carbon dioxide, 1234yf, and1234ze(E) and satisfying Expressions A to Expression E is referred to asa working fluid (R1).

(A) A self-decomposition reaction is not caused at 215° C. and at 10MPaG.

(B) A combustion speed is less than 10 cm/sec.

(C) A relative pressure (RDP_(R410)A) expressed by Expression (Z) belowis less than 1.78.

$\begin{matrix}{{{Relative}\mspace{14mu} {pressure}\mspace{14mu} \left( {RDP}_{R\; 410A} \right)} = \frac{\begin{matrix}{{Compressor}\mspace{14mu} {discharge}\mspace{14mu} {gas}} \\{{pressure}\mspace{14mu} {of}\mspace{14mu} {sample}\mspace{14mu} \left( {DP}_{sample} \right)}\end{matrix}}{\begin{matrix}{{Compressor}\mspace{14mu} {discharge}\mspace{14mu} {gas}} \\{{pressure}\mspace{14mu} {of}\mspace{14mu} R\; 410A\mspace{14mu} \left( {DP}_{R\; 410A} \right)}\end{matrix}}} & (Z)\end{matrix}$

In Expression (Z), R410A indicates a mixture of R32 andpentafluoroethane (HFC-125 or R-125, or to be also referred to as R125)at a mass ratio of 1:1 and a sample indicates a working fluid to beevaluated relatively. Compressor discharge gas pressures of the sampleand R410A are compressor discharge gas pressures obtained when operatingthe standard refrigeration cycle system under the above-describedtemperature condition (T) using the sample and R410A.

(D) Relative refrigerating capacity (RQ_(R410A)) expressed by Expression(X) below exceeds 0.91.

$\begin{matrix}{{{Relative}\mspace{14mu} {refrigerating}\mspace{14mu} {capacity}\mspace{14mu} \left( {RQ}_{R\; 410A} \right)} = \frac{{Refrigerating}\mspace{14mu} {capacity}\mspace{14mu} {of}\mspace{14mu} {sample}\mspace{14mu} \left( Q_{sample} \right)}{{Refrigerating}\mspace{14mu} {capacity}\mspace{14mu} {of}\mspace{14mu} R\; 410A\mspace{14mu} \left( Q_{R\; 410A} \right)}} & (X)\end{matrix}$

In Expression (X), R410A is the same as that in Expression (Z) and asample indicates a working fluid to be evaluated relatively.Refrigerating capacities of the sample and R410A are outputs (kW)obtained when operating the standard refrigeration cycle system underthe above-described temperature condition (T) using the sample andR410A.

(E) The global warming potential (100 years) in the IntergovernmentalPanel on Climate Change (IPCC) Fourth Assessment Report is less than160. In the following explanation, the above-described global warmingpotential is also referred to as “GWP.”

The first working fluid obtains the properties equivalent to those of(A) to (E) above by containing the working fluid (R1) having theabove-described properties of (A) to (E) by 90 to 100 mass % relative tothe total amount of the working fluid. The first working fluid has theabove-described temperature glide property in addition to theseproperties, to thereby obtain cycle performance replaceable with that ofR410A, and at the same time, have a small burden on an apparatus, lowflammability, suppressed self-decomposition, and less effect on globalwarming, and therefore, be usable stably even if leaked.

In the present invention, in order to bring each of the above-describedproperties to a satisfactory level, the combination of HFO-1123 and R32is selected, and further the composition combining with at least oneselected from R152a, R161, propane, propylene, carbon dioxide, 1234yf,and 1234ze(E) is selected. Then, in the mixture composed of HFO-1123,R32, and at least one selected from R152a, R161, propane, propylene,carbon dioxide, 1234yf, and 1234ze(E), the working fluid (R1) having thecomposition satisfying the above-described properties of (A) to (E) isfound out. Incidentally, in the working fluid (R1), the temperatureglide is preferred to be 10° C. or less, and the working fluid (R1)having the temperature glide of 10° C. or less is usable as the firstworking fluid as it is.

The second working fluid is a working fluid in which the content ratiosof HFO-1123, R32, and at least one selected from R152a, R161, propane,propylene, carbon dioxide, 1234yf, and 1234ze(E) are adjusted so as toobtain a property not causing the self-decomposition reaction under astricter condition while maintaining the other properties as compared tothe first working fluid.

The second working fluid contains a working fluid (to be referred to asa working fluid (R2) hereinafter) having a composition composed of onlyHFO-1123, R32, and at least one selected from R152a, R161, propane,propylene, carbon dioxide, 1234yf, and 1234ze(E) and satisfyingExpression A2, Expression B, Expression C, Expression D, and ExpressionE by 90 to 100 mass % relative to the total amount of the working fluid.

The working fluid (R2) has the above-described properties of (B) to (E)and further has a property of (A2) in which the self-decompositionreaction is not caused under a condition stricter than (A) describedabove and pyrolyzed products resulting from an ignition test are smallerthan those of (A) described above.

The second working fluid obtains the properties equivalent to those of(A2) and (B) to (E) above by containing the working fluid (R2) havingthe above-described properties of (A2) and (B) to (E) by 90 to 100 mass% relative to the total amount of the working fluid. The second workingfluid has the above-described temperature glide property in addition tothese properties, to thereby obtain cycle performance replaceable withthat of R410A, and at the same time, have a small burden on anapparatus, low flammability, suppressed self-decomposition, and lesseffect on global warming, and therefore, be usable stably even ifleaked. Incidentally, in the working fluid (R2) itself as well, thetemperature glide is preferred to be 10° C. or less, and the workingfluid (R2) having the temperature glide of 10° C. or less is usable asthe second working fluid as it is. Hereinafter, the working fluid (R1)and the working fluid (R2) will be explained.

In Table 1, properties of HFO-1123, R32, R152a, R161, propane,propylene, carbon dioxide, 1234yf, and 1234ze(E) as a single compound,reference values of (A) to (E) described above in the properties, and areference value of the temperature glide in the working fluid of thepresent invention are illustrated, together with properties of R410A asthe working fluid. Incidentally, RCOP_(R410A) illustrated in Table 1 isa relative coefficient of performance with respect to R410A expressed byExpression (Y) below. In the working fluid, RCOP_(R410A) is preferred tobe greater than 0.9.

$\begin{matrix}{{{Relative}\mspace{14mu} {coefficient}\mspace{14mu} {of}\mspace{14mu} {performance}\mspace{14mu} \left( {RCOP}_{R\; 410A} \right)} = \frac{{Coefficient}\mspace{14mu} {of}\mspace{14mu} {performance}\mspace{14mu} {of}\mspace{14mu} {sample}\mspace{14mu} \left( {COP}_{sample} \right)}{{Coefficient}\mspace{14mu} {of}\mspace{14mu} {performance}\mspace{14mu} {of}\mspace{14mu} R\; 410A\mspace{14mu} \left( {COP}_{R\; 410A} \right)}} & (Y)\end{matrix}$

In Expression (Y), R410A is the same as that in Expression (Z), and asample indicates a working fluid to be evaluated relatively.Coefficients of performance of the sample and R410A are coefficients ofperformance obtained when operating the standard refrigeration cyclesystem under the above-described temperature condition (T) using thesample and R410A.

TABLE 1 Self Compound/ decomposition Combustion Temperature Evaluation(215° C., speed glide item [Unit] GWP 10MPaG) [cm/sec] RCOP_(R410A)RQ_(R410A) [° C.] RDP_(R410A) Reference <160 Absent <10 >0.9 >0.91 ≤10<1.78 value R410A 2088.0 Absent Non flammable 1.00 1.00 0.1 1.00HFO-1123 0.3 Present 6.6 0.92 1.11 0.0 1.25 R32 675.0 Absent 6.7 1.021.09 0.0 1.02 1234yf 4.0 Absent 1.5 1.03 0.41 0.0 0.42 1234ze(E) 6.0Absent Non flammable 1.07 0.32 0.0 0.32 Carbon dioxide 1.0 Absent Nonflammable — — 0.0 — R152a 124.0 Absent 23.5 1.10 0.41 0.0 0.38 R161 12.0Absent 38.3 1.07 0.61 0.0 0.56 Propane 3.3 Absent 43.0 1.05 0.58 0.00.57 Propylene 1.8 Absent 47.0 1.04 0.70 0.0 0.68[−]; Carbon dioxide is brought into a supercritical state at thecondensation temperature, and thus RCOP_(410A), RQ_(R410A), andRDP_(R410A) are incalculable.

There will be explained the respective components contained in theworking fluid (R1) and the working fluid (R2) using Table 1.Incidentally, Table 1 does not include a column where the property of(A2) is described, but the condition of the self-decomposition of (A2)is stricter than that of (A). Even under the condition of (A2), onlyHFO-1123 has the self-decomposition and the components other than thatdo not have the self-decomposition.

HFO-1123 and R32 can be cited as the component having the cycleperformance replaceable with that of R410A from Table 1. However,HFO-1123 has the self-decomposition and R32 has a high GWP. Here, thecombination of HFO-1123 and R32 fails to satisfy the self-decompositionor the GWP out of the above-described properties of (A), (A2), (B) to(E), the temperature glide, and RCOP_(R410A) in any composition.

Thus, in the present invention, as a compound or a combination ofcompounds that has a GWP lower than that of R32, is capable ofsuppressing the self-decomposition of HFO-1123, and further does notimpair the other properties, one or more selected from R152a, R161,propane, propylene, carbon dioxide, 1234yf, and 1234ze(E) are selectedto find out an appropriate composition in the combination of HFO-1123and R32. The above-described properties of (A), (A2), and (B) to (E)will be explained together with Expression A, Expression A2, andExpression B to Expression E. Further, RCOP_(R410A) and the temperatureglide will be explained.

[Self-Decomposition]

The properties of (A) and (A2) are properties relating to theself-decomposition. HFO-1123 contained in the working fluid (R1) and theworking fluid (R2) has self-decomposition. The self-decomposition can besuppressed by kinds of components composing the working fluid (R1) andthe working fluid (R2) together with HFO-1123 and the content ratios ofthe respective components (to be referred to as a “composition”hereinafter) of the working fluid (R1) and the working fluid (R2). Theself-decomposition of the working fluid is required to be suppressedunder the condition of high temperature and high pressure in excess ofranges of temperature and pressure to be used normally as the workingfluid.

In the working fluid (R1), the composition satisfies Expression A,thereby not causing the self-decomposition reaction under the conditionof temperature of 215° C. and pressure of 10 MPaG in aself-decomposition test to be evaluated by the following method.Incidentally, MPaG being the unit of pressure indicates MPa in terms ofgauge pressure.

Expression A is expressed by“0<−1.000×[HFO-1123]+1.179×[R32]+1.316×[1234yf]+1.316×[1234ze(E)]+3.831×[CO2]+2.632×[R152a]+2.390×[R161]+6.262×[propane]+2.237×[propylene].”In Expression A, regarding coefficients to multiply the content ratiosof the compounds, the negative coefficient indicates how easily thecompound causes the self-decomposition and the positive coefficientindicates how easily the compound suppresses the self-decomposition. Acompound having a larger coefficient means suppression of theself-decomposition of HFO-1123 by a smaller content.

In the working fluid (R2), the composition satisfies Expression A2, andthereby, as compared to the working fluid (R1), a composition with asmaller content ratio of HFO-1123 is made and use under a strictercondition of the self-decomposition is enabled. The compositionsatisfies Expression A2, and thereby a less amount of pyrolyzed productis generated at the ignition test as compared to (A) above.

0<−1.000×[HFO-1123]+1.033×[R32]+0.896×[1234yf]+0.896×[1234ze(E)]+2.891×[CO2]+1.955×[R152a]+1.410×[R161]+3.737×[propane]+1.520×[propylene]  ExpressionA2;

<Self-Decomposition Test>

The self-decomposition test is conducted using a facility compliant withthe A method recommended as a facility for measuring a combustion rangeof gas made by mixing gas containing halogen in an individualnotification in High Pressure Gas Safety Act.

Concretely, a working fluid to be a sample is enclosed, to apredetermined pressure, within a spherical pressure tight case having aninternal volume of 650 cm³ controlled to a predetermined temperaturefrom the outside, and then an energy of about 30 J is applied thereto byfusing a platinum wire installed therein. The temperature and pressurechanges in the pressure tight case occurring after the application aremeasured, thereby making it possible to confirm presence or absence ofthe self-decomposition reaction. When a pressure rise is less than 1MPaG, absence of self-decomposition reaction is determined under thecondition of this temperature and pressure.

<Ignition Test>

The ignition test is conducted by measuring the amount of pyrolyzedproduct of the working fluid to be a sample after the same test as theabove-described self-decomposition test (temperature of 215° C. andpressure of 10 MPaG) is conducted. The case where the amount ofpyrolyzed product is smaller than that obtained when a mixture ofHFO-1123 and R32 to be 0=−1.000×[HFO-1123]+1.033×[R32] is subjected tothe test is determined to satisfy the reference of (A2).

[Combustion Speed]

The property (B) is a property relating to the flammability and thecomposition satisfying Expression B is made, and thereby the combustionspeed of each of the working fluid (R1) and the working fluid (R2)becomes less than 10 cm/sec. As is clear from Table 1, carbon dioxide,1234yf, and 1234ze(E) are nonflammable or have a small combustion speedand the combustion speed of each of R152a, R161, propane, and propyleneis as large as 10 cm/sec or more. In terms of the combustion speed,using carbon dioxide, 1234yf, and 1234ze(E) is preferred, but in termsof the other properties, for example, carbon dioxide tends to increasethe burden on an apparatus because its compressor discharge gas pressureis high, which is not illustrated in Table 1, and 1234yf and 1234ze(E)are low in RQ_(R410A), each have a small coefficient in Expression A andExpression A2 above, and have a low ability to suppress theself-decomposition of HFO-1123.

Expression B is an expression for bringing the combustion speed of theworking fluid to less than 10 cm/sec when using such carbon dioxide,1234yf, 1234ze(E), R152a, R161, propane, and propylene in combinationwith HFO-1123 and R32.

Expression B is expressed by“10>3.426×[HFO-1123]+5.673×[R32]+2.193×[1234yf]−0.596×[1234ze(E)]−0.768×[CO2]+29.897×[R152a]+64.400×[R161]+118.965×[propane]+94.943×[propylene].”In Expression B, regarding coefficients to multiply the content ratiosof the compounds, the positive coefficient indicates ease of combustionand the negative coefficient indicates a suppression effect ofcombustion.

The combustion speed of each of the working fluid (R1) and the workingfluid (R2) is preferably less than 8 cm/sec, more preferably less than 6cm/sec, and further preferably less than 4 cm/sec. In this case, thecomposition only needs to be adjusted so as to satisfy Expression B2,Expression B3, and Expression B4 below in which the numeral to the leftof the inequality sign in Expression B is set to 8, 6, and 4respectively. As the combustion speed is lower, the working fluidbecomes more excellent having high safety. Incidentally, the combustionspeed is a combustion speed measured at a temperature of 23° C. based onIOS817: 2014.

8>3.426×[HFO-1123]+5.673×[R32]+2.193×[1234yf]−0.596×[1234ze(E)]−0.768×[CO2]+29.897×[R152a]+64.400×[R161]+118.965×[propane]+94.943×[propylene]  ExpressionB2;

6>3.426×[HFO-1123]+5.673×[R32]+2.193×[1234yf]−0.596×[1234ze(E)]−0.768×[CO2]+29.897×[R152a]+64.400×[R161]+118.965×[propane]+94.943×[propylene]  ExpressionB3;

4>3.426×[HFO-1123]+5.673×[R32]+2.193×[1234yf]−0.596×[1234ze(E)]−0.768×[CO2]+29.897×[R152a]+64.400×[R161]+118.965×[propane]+94,943×[propylene]  ExpressionB4;

[RDP_(R410A)]

The property (C) is a property relating to the burden on an apparatus.RDP_(R410A) is an index indicating the burden on the apparatus of theworking fluid by a relative comparison with a burden on an apparatus ofR410A as a replacement object. RDP_(R410A) is, as described inExpression (Z) above, described by a value of a ratio of the compressordischarge gas pressure (DP_(sample)) when operating the standardrefrigeration cycle under the above-described temperature condition (T)by using the working fluid (sample) to the compressor discharge gaspressure (DP_(R410)A) when operating the standard refrigeration cycleunder the above-described temperature condition (T) by using R410A.

The compressor discharge gas pressure indicates the maximum pressure inthe standard refrigeration cycle under the above-described temperaturecondition (T), and it is possible to expect the degree of a pressureburden on the apparatus when actually operating a heat cycle system of arefrigerating apparatus, an air-conditioning apparatus, or the like byusing the working fluid based on this value. Incidentally, RDP_(R410A)is found by a later-described method concretely.

The composition of the working fluid is designed to be a compositionsatisfying Expression C, thereby making it possible to obtain theworking fluid (R1) and the working fluid (R2) each having RDP_(R410A)being less than 1.78. The working fluid (R1) and the working fluid (R2)each have RDP_(R410A) being less than 1.78, and thereby the pressureburden on the apparatus does not increase greatly when a predeterminedapparatus operates the heat cycle system under predetermined conditionsby using the working fluid as compared to the case where the sameapparatus operates the heat cycle system under the same conditions byusing R410A. That is, the composition of each of the working fluid (R1)and the working fluid (R2) satisfies Expression C, and thereby using theworking fluid (R1) and the working fluid (R2) for the apparatus usingR410A as the working fluid is almost possible without a large designchange.

Expression C is expressed by“1.78>1.293×[HFO-1123]+1.029×[R32]+0.369×[1234yf]+0.354×[1234ze(E)]+3.807×[CO2]+0.229×[R152a]+0.406×[R161]+0.568×[propane]+0.719×[propylene].”

In Expression C, regarding coefficients to multiply the content ratiosof the compounds, the coefficient larger than 1 means that RDP_(R410)Ais greater than 1, namely, the compressor discharge gas pressure islarger than that of R410A, and as the value is larger, the correspondingcompound increases the burden on the apparatus of the working fluid tobe obtained. The coefficient smaller than 1 means that RDP_(R410A) isless than 1, namely the compressor discharge gas pressure is smallerthan that of R410A, and as the value is smaller, the correspondingcompound can reduce the burden on the apparatus of the working fluid tobe obtained.

RDP_(R410A) of each of the working fluid (R1) and the working fluid (R2)is preferably less than 1.74, more preferably less than 1.65, furtherpreferably less than 1.4, and still further preferably less than 1.2.Incidentally, the lower limit of RDP_(R410A) of each of the workingfluid (R1) and the working fluid (R2) is not limited in particular. Inthis case, the composition only needs to be adjusted so as to satisfyExpression C2, Expression C3, Expression C4, and Expression C5 below inwhich the numeral to the left of the inequality sign in Expression C isset to 1.74, 1.65, 1.4, and 1.2 respectively.

1.74>1.293×[HFO-1123]+1.029×[R32]+0.369×[1234yf]+0.354×[1234ze(E)]+3.807×[CO2]+0.229×[R152a]+0.406×[R161]+0.568×[propane]+0.719×[propylene]  ExpressionC2;

1.65>1.293×[HFO-1123]+1.029×[R32]+0.369×[1234 yf]+0.354×[1234ze(E)]+3.807×[CO2]+0.229×[R152a]+0.406×[R161]+0.568×[propane]+0.719×[propylene]  ExpressionC3;

1.4>1.293×[HFO-1123]+1.029×[R32]+0.369×[1234 yf]+0.354×[1234ze(E)]+3.807×[CO2]+0.229×[R152a]+0.406×[R161]+0.568×[propane]+0.719×[propylene]  ExpressionC4;

1.2>1.293×[HFO-1123]+1.029×[R32]+0.369×[1234 yf]+0.354×[1234ze(E)]+3.807×[CO2]+0.229×[R152a]+0.406×[R161]+0.568×[propane]+0,719×[propylene]  ExpressionC5;

[RQ_(R410A)]

The property (D) is a property relating to the refrigerating capacity(Q) in a refrigeration cycle system. The cycle performance required forapplication of the working fluid to the heat cycle is evaluated by thecoefficient of performance and capacity. In the case of the heat cyclesystem being the refrigeration cycle system, the capacity is therefrigerating capacity, and the refrigerating capacity (Q) is an output(kW) in the refrigeration cycle system. RQ_(R410A) is an indexindicating the refrigerating capacity (Q) of the working fluid by arelative comparison with the refrigerating capacity (Q) of R410A as areplacement object. Incidentally, RQ_(R410A) is found by alater-described method concretely.

In the working fluid containing the above-described compounds, thecomposition is designed to be a composition satisfying Expression D, andthereby the working fluid (R1) and the working fluid (R2) each havingRQ_(R410A) greater than 0.91 are obtained, resulting in that therefrigerating capacity does not decrease greatly as compared to R410A.

Expression D is expressed by“0.91<1.214×[HFO-1123]+1.133×[R32]+0.402×[1234yf]+0.346×[1234ze(E)]+3.359×[CO2]+0.323×[R152a]+0.548×[R161]+0.588×[propane]+0.725×[propylene].”

In Expression D, regarding coefficients to multiply the content ratiosof the compounds, the coefficient larger than 1 means that RQ_(R410A) isgreater than 1, namely, the refrigerating capacity is larger than thatof R410A, and as the value is larger, the corresponding compound cancontribute to an improvement in the refrigerating capacity of theworking fluid to be obtained. The coefficient smaller than 1 means thatRQ_(R410A) is less than 1, namely the refrigerating capacity is smallerthan that of R410A, and as the value is smaller, the correspondingcompound reduces the refrigerating capacity of the working fluid to beobtained.

RQ_(R410A) of each of the working fluid (R1) and the working fluid (R2)is preferably greater than 0.95 and more preferably greater than 1. Inthis case, the composition only needs to be adjusted so as to satisfyExpression D2 and Expression D3 below in which the numeral to the leftof the inequality sign in Expression D is set to 0.95 and 1respectively. Incidentally, the upper limit of RQ_(R410A) of each of theworking fluid (R1) and the working fluid (R2) is not limited inparticular.

0.95<1.214×[HFO-1123]+1.133×[R32]+0.402×[1234 yf]+0.346×[1234ze(E)]+3.359×[CO2]+0,323×[R152a]+0.548×[R161]+0.588×[propane]+0.725×[propylene]  ExpressionD2;

1<1.214×[HFO-1123]+1.133×[R32]+0.402×[1234 yf]+0.346×[1234ze(E)]+3.359×[CO2]+0.323×[R152a]+0.548×[R161]+0.588×[propane]+0.725×[propylene]  ExpressionD3;

[GWP]

The property (E) is a property relating to the GWP being an indexmeasuring the effect of the working fluid on the global warming.Expression E is an expression indicating that the GWP in the workingfluid is a weighted average of composition masses and the GWP found bythe weighted average satisfies less than 160. The GWP of R410A, which isa replacement of the working fluid of the present invention, is 2088 togreatly affect the global environment. On the other hand, the GWP ofeach of the working fluid (R1) and the working fluid (R2) is less than160 to less affect the global environment.

Expression E is expressed by“160>0.3×[HFO-1123]+675×[R32]+4×[1234yf]+6×[1234ze(E)]+1×[CO2]+124×[R152a]+12×[R161]+3.3×[propane]+1.8×[propylene].”

As described above, coefficients to multiply the content ratios of thecompounds in Expression E each are a GWP of each of the compoundsindependently. It is clear also from Expression E that R32 causes anincrease in the GWP of the working fluid. The working fluid (R1) and theworking fluid (R2) each are that the GWP is reduced and the otherproperties are maintained by partially replacing R32 that has goodproperties but is high in the GWP with another compound in the workingfluid using HFO-1123 and R32 that is excellent in performance as aworking fluid replaceable with conventional R410A.

The GWP of each of the working fluid (R1) and the working fluid (R2) ispreferably less than 150, more preferably less than 120, furtherpreferably less than 100, and still more preferably less than 70. Inthis case, the composition only needs to be adjusted so as to satisfyExpression E2, Expression E3, Expression E4, and Expression E5 below inwhich the numeral to the left of the inequality sign in Expression E isset to 150, 120, 100, and 70 respectively.

150>0.3×[HFO-1123]+675×[R32]+4×[1234 yf]+6×[1234ze(E)]+1×[CO2]+124×[R152a]+12×[R161]+3.3×[propane]+1.8×[propylene]  ExpressionE2;

120>0.3×[HFO-1123]+675×[R32]+4×[1234 yf]+6×[1234ze(E)]+1×[CO2]+124×[R152a]+12×[R161]+3.3×[propane]+1.8×[propylene]  ExpressionE3;

100>0.3×[HFO-1123]+675×[R32]+4×[1234 yf]+6×[1234ze(E)]+1×[CO2]+124×[R152a]+12×[R161]+3.3×[propane]+1.8×[propylene]  ExpressionE4;

70>0.3×[HFO-1123]+675×[R32]+4×[1234 yf]+6×[1234ze(E)]+1×[CO2]+124×[R152a]+12×[R161]+3.3×[propane]+1.8×[propylene]  ExpressionE5;

[RCOP_(R410A)]

The working fluid (R1) and the working fluid (R2) each have the property(D), and thereby the cycle performance becomes equivalent to that ofR410A. Normally, the cycle performance of the working fluid depends onthe capacity and the coefficient of performance. The coefficient ofperformance (COP) is a value obtained by dividing an output (kW) bymotive power (kW) consumed to obtain the output (kW), which correspondsto energy consumption efficiency. As the value of the coefficient ofperformance is higher, it becomes possible to obtain a large output by asmall input.

In the working fluid (R1), the working fluid (R2), and the working fluidof the present invention that contains one of the working fluid (R1) andthe working fluid (R2) at a ratio of 90 to 100 mass %, RCOP_(R410A) ispreferred to be greater than 0.9, more preferably greater than 0.95, andfurther preferably greater than 1.

[Temperature Glide]

The working fluid of the present invention has a temperature glide of10° C. or less when operating the standard refrigeration cycle systemunder the above-described temperature condition (T). Further, theworking fluid (R1) and the working fluid (R2) each preferably have atemperature glide of 10° C. or less similarly. When a mixture is used asthe working fluid, the mixture is preferred to be an azeotropic mixtureor a pseudoazeotropic mixture such as R410A. A zeotropic composition hasa problem of undergoing a composition change when put into arefrigerating and air-conditioning apparatus from a pressure container.Further, when a refrigerant leaks out from a refrigerating andair-conditioning apparatus, a refrigerant composition in therefrigerating and air-conditioning apparatus is highly likely to change,resulting in difficulty in recovery of the refrigerant composition to aninitial state. In the meantime, the above-described problems can beavoided as long as the working fluid is an azeotropic orpseudoazeotropic mixture.

As an index to indicate the properties of the working fluid, the“temperature glide” is commonly used. The temperature glide is definedas properties that the initiation temperature and the completiontemperature of a heat exchanger, for example, of evaporation in anevaporator or of condensation in a condenser differ from each other. Thetemperature glide of an azeotropic mixture refrigerant is 0, and thetemperature glide of such a pseudoazeotropic mixture refrigerant asR410A is extremely close to 0.

The case of the temperature glide being large is a problem because, forexample, an inlet temperature of an evaporator decreases, to makefrosting more likely to occur. Further, in the heat cycle system, inorder to improve heat exchange efficiency, it is common to make theworking fluid flowing in a heat exchanger and a heat source fluid suchas water or the air flow in counter-current flow, and the temperaturedifference of the heat source fluid is small in a stable operationstate, and therefore, it is difficult to obtain a heat cycle system withgood energy efficiency when the working fluid is a zeotropic mixedmedium with a large temperature glide. Therefore, the zeotropic mixedmedium with an appropriate temperature glide is desired.

HFO-1123 and R32 to be used for the working fluid of the presentinvention are a pseudoazeotropic mixture close to an azeotropic mixture,when contained within a composition range of 99:1 to 1:99 in mass ratio.That is, the temperature glide is substantially 0 even when HFO-123 andR32 are combined with any composition. Thus, when the temperature glideis set to 10° C. or less, it is not particularly necessary to considerthe content ratio of R32 to HFO-1123 to be used for the working fluid.The kinds and the compositions of R152a, R161, propane, propylene,carbon dioxide, 1234yf, and 1234ze(E) that are used together withHFO-1123 and R32 are adjusted so that the temperature glide becomes 10°C. or less.

Incidentally, the temperature glide of each of the working fluid of thepresent invention and the working fluid (R1) and the working fluid (R2)is preferably 8° C. or less, more preferably 6° C. or less, and furtherpreferably 4° C. or less.

As the standard refrigeration cycle system to be used to evaluateRDP_(R410A), RQ_(R410A), RCOP_(R410A), and the temperature glidedescribed above, a refrigeration cycle system whose schematicconfiguration diagram is illustrated in FIG. 1 is cited, for example.Hereinafter, there will be explained methods of finding therefrigerating capacity and the coefficient of performance of apredetermined working fluid using the refrigeration cycle systemillustrated in FIG. 1.

A refrigeration cycle system 10 illustrated in FIG. 1 is a systemschematically configured to include: a compressor 11 that compressesworking fluid vapor A to make it into working fluid vapor B at hightemperature and high pressure; a condenser 12 that cools and liquefiesthe working fluid vapor B emitted from the compressor 11 to make it intoa working fluid C at low temperature and high pressure; an expansionvalve 13 that expands the working fluid C emitted from the condenser 12to make it into a working fluid D at low temperature and low pressure;an evaporator 14 that heats the working fluid D emitted from theexpansion valve 13 to make it into the working fluid vapor A at hightemperature and low pressure; a pump 15 that supplies load fluid E tothe evaporator 14; and a pump 16 that supplies fluid F to the condenser12.

In the refrigeration cycle system 10, the cycle of (i) to (iv) below isrepeated.

(i) Compressing the working fluid vapor A emitted from the evaporator 14in the compressor 11 to make it into the working fluid vapor B at hightemperature and high pressure (hereinafter, to be referred to as an “ABprocess”).(ii) Cooling and liquefying the working fluid vapor B emitted from thecompressor 11 by the fluid F in the condenser 12 to make it into theworking fluid C at low temperature and high pressure. In this event, thefluid F is heated to be made into fluid F′ and emitted from thecondenser 12 (hereinafter, to be referred to as a “BC process”).(iii) Expanding the working fluid C emitted from the condenser 12 in theexpansion valve 13 to make it into the working fluid D at lowtemperature and low pressure (hereinafter, to be referred to as a “CDprocess”).(iv) Heating the working fluid D emitted from the expansion valve 13 bythe load fluid E in the evaporator 14 to make it into the working fluidvapor A at high temperature and low pressure. In this event, the loadfluid E is cooled to be made into load fluid E′ and emitted from theevaporator 14 (hereinafter, to be referred to as a “DA process”).

The refrigeration cycle system 10 is a cycle system achieved by anadiabatic and isoentropic change, an isenthalpic change, and an isobaricchange. The change of state of the working fluid can be expressed as atrapezoid having A, B, C, and D as vertices when the change isillustrated on a pressure-enthalpy line (curve) diagram illustrated inFIG. 2.

The AB process is a process of performing adiabatic compression in thecompressor 11 to make the working fluid vapor A at high temperature andlow pressure into the working fluid vapor B at high temperature and highpressure, and is indicated by an AB line in FIG. 2. As will be describedlater, the working fluid vapor A is introduced, in a superheated state,into the compressor 11, and therefore the working fluid vapor B to beobtained therein is vapor also in a superheated state. The compressordischarge gas pressure (discharge pressure) used for calculatingRDP_(R410A) described above is a pressure (DP) in the state of B in FIG.2 and is the highest pressure in the refrigeration cycle. Incidentally,the temperature in the state of B in FIG. 2 is a compressor dischargegas temperature (discharge temperature) and is the highest temperaturein the refrigeration cycle.

The BC process is a process of performing isobaric cooling in thecondenser 12 to make the working fluid vapor B at high temperature andhigh pressure into the working fluid vapor C at low temperature and highpressure, and is indicated by a BC line in FIG. 2. The pressure in thisevent is the condensation pressure. An intersection point T₁ on a highenthalpy side of intersection points of the pressure-enthalpy line andthe BC line is a condensation temperature (an average temperature of thecondensation start temperature and the condensation completiontemperature in the case of the working fluid being a zeotropic mixture),and an intersection point T₂ on a low enthalpy side is a condensationboiling temperature. Here, the temperature glide in the case of theworking fluid being a composition composed of a plurality of compoundsis illustrated as the difference between T₁ and T₂.

The CD process is a process of performing isenthalpic expansion in theexpansion valve 13 to make the working fluid C at low temperature andhigh pressure into the working fluid D at low temperature and lowpressure, and is indicated by a CD line in FIG. 2. Incidentally, whenthe temperature at the working fluid C at low temperature and highpressure is indicated by T₃, T₂−T₃ is a degree of supercooling (SC) ofthe working fluid in the cycle of (i) to (iv).

The DA process is a process of performing isobaric heating in theevaporator 14 to return the working fluid D at low temperature and lowpressure to the working fluid vapor A at high temperature and lowpressure, and is indicated by a DA line in FIG. 2. The pressure in thisevent is the evaporation pressure. An intersection point T₆ on a highenthalpy side of intersection points of the pressure-enthalpy line andthe DA line is an evaporation temperature (an average temperature of theevaporation start temperature and the evaporation completion temperaturein the case of the working fluid being a zeotropic mixture). When thetemperature of the working fluid vapor A is indicated by T₇, T₇−T₆ is adegree of superheating (SH) of the working fluid in the cycle of (i) to(iv). Incidentally, T₄ indicates the temperature of the working fluid D.

Q and COP of the working fluid are obtained from Equations (11) and (12)below respectively when using enthalpies h_(A), h_(B), h_(C), and h_(D)in respective states of A (after evaporation, high temperature and lowpressure), B (after compression, high temperature and high pressure), C(after condensation, low temperature and high pressure), and D (afterexpansion, low temperature and low pressure) of the working fluid. It isassumed that there is no loss due to equipment efficiency and nopressure loss in pipes and heat exchangers.

The thermodynamic property required for calculation of the cycleperformance of the working fluid can be calculated based on ageneralized state equation (Soave-Redlich-Kwong equation) based on aprinciple of corresponding states, and on thermodynamic relationalexpressions. When the characteristic value cannot be obtained,calculation is performed using an estimation method based on an atomicgroup contribution method.

Q=h _(A) −h _(D)  (11)

COP=Q/compression work=(h _(A) −h _(D))/(h _(B) −h _(A))  (12)

Q expressed by (h_(A)−h_(D)) above corresponds to the output (kW) of therefrigeration cycle, and the compression work expressed by(h_(B)−h_(A)), for example, electric energy required to operate thecompressor corresponds to the consumed motive power (kW). Further, Qmeans the capability of refrigerating the load fluid, and a higher Qmeans that the same heat cycle system can perform a larger amount ofwork. In other words, having a high Q indicates that a targetperformance can be obtained by a small amount of working fluid, thusenabling downsizing of the heat cycle system.

Here, the concrete composition of each of the working fluid (R1) and theworking fluid (R2) is preferably a composition composed of threecomponents or four components of HFO-1123, R32, and one or two selectedfrom R152a, R161, propane, propylene, carbon dioxide, 1234yf, and1234ze(E) and satisfying the above-described conditions and morepreferably a composition composed of four components.

The composition of each of the working fluid (R1) and the working fluid(R2) is more preferably a composition composed of four components ofHFO-1123, R32, one selected from R152a, R161, propane, and propylene,and one selected from carbon dioxide, 1234yf, and 1234ze(E) andsatisfying the above-described conditions.

There are described concrete examples of combinations of theabove-described preferred compounds in the working fluid (R1) and theworking fluid (R2) in (1) to (12) below. However, regarding thefollowing compositions of four components, the case where the content ofone of the two selected from R152a, R161, propane, propylene, carbondioxide, 1234yf, and 1234ze(E) is “0,” namely the case where thecomposition is composed of three components may be included, but thecomposition composed of four components is more preferred.

(1) HFO-1123, R32, R152a, carbon dioxide

(2) HFO-1123, R32, R152a, 1234yf

(3) HFO-1123, R32, R152a, 1234ze(E)

(4) HFO-1123, R32, R161, carbon dioxide

(5) HFO-1123, R32, R161, 1234yf

(6) HFO-1123, R32, R161, 1234ze(E)

(7) HFO-1123, R32, propane, carbon dioxide

(8) HFO-1123, R32, propane, 1234yf

(9) HFO-1123, R32, propane, 1234ze(E)

(10) HFO-1123, R32, propylene, carbon dioxide

(11) HFO-1123, R32, propylene, 1234yf

(12) HFO-1123, R32, propylene, 1234ze(E)

When each of the working fluid (R1) and the working fluid (R2) iscomposed of such four components, the content ratios of these fourcomponents are found as in the following examples, for example. Thefollowings are examples of the case of finding the compositionsatisfying Expression A to Expression E with the above-describedcombination of (4). The composition satisfying Expression A toExpression E can be found in the same manner also in the case of theother four components, namely even with the above-described combinationsof (1) to (3) and (5) to (12), Further, the same is true of the case offinding compositions satisfying Expression A2, and Expression B toExpression E.

The composition composed of HFO-1123, R32, carbon dioxide, and R161 andsatisfying Expression A to Expression E is found by using, for example,a triangular coordinate chart of HFO-1123, carbon dioxide, and R161illustrated in FIG. 3 in which the content of R32 is set to a fixedcontent (in FIG. 3, the ratio of R32 is 22 mass % relative to the totalamount of HFO-1123, R32, carbon dioxide, and R161 (100 mass %)). In FIG.3, “∘” indicates a composition satisfying all of Expression A toExpression E and “x” indicates a composition not satisfying at least oneof Expression A to Expression E.

In FIG. 3, Expression A to Expression E are satisfied within aquadrangular composition range surrounded by a straight line indicatingthe content of R161 being 0, a dotted line A for satisfying ExpressionA, a dot and dash line B for satisfying Expression B, and a broken lineC for satisfying Expression C. A composition range in which Expression Ais satisfied ranges in the direction of an arrow Da from the dotted lineA, a composition range in which Expression B is satisfied ranges in thedirection of an arrow Db from the dot and dash line B similarly, acomposition range where Expression C is satisfied ranges in thedirection of an arrow Dc from the broken line C, and a composition rangewhere Expression D is satisfied ranges in the direction of an arrow Ddfrom a two-dot chain line D. When R32 is 22 mass %, [R32] is 0.22 andExpression E is achieved regardless of the content ratios of HFO-1123,carbon dioxide, and R161. An arrow De means that Expression E isachieved in the entire region of the triangular coordinate chart.Incidentally, the boundary line of Expression E is illustrated on thestraight line indicating the content of carbon dioxide being 0 forconvenience.

When a triangular coordinate chart similar to the above is formed underthe condition that the content ratio of R32 is different from the above,for example, the ratio of R32 to the total amount of HFO-1123, R32,carbon dioxide, and R161 (100 mass %) is 15 mass %, a composition rangewhere Expression A to Expression E are satisfied when the ratio of R 32is 15 mass % can be found on the triangular coordinate chart. Triangularcoordinate charts are formed while varying the content of R32 to thetotal amount of HFO-1123, R32, carbon dioxide, and R161 (100 mass %) asabove and these triangular coordinate charts are integrated, therebyobtaining the composition of the working fluid (R1) that is composed ofthe above-described four components (4) of HFO-1123, R32, R161, andcarbon dioxide and satisfies Expression A to Expression E.

(Working Fluid of the Present Invention)

The first working fluid contains, as described above, HFO-1123, R32, andat least one selected from R152a, R161, propane, propylene, carbondioxide, 1234yf, and 1234ze(E) at the content ratios satisfyingExpression A to Expression E so that the total content of them becomes90 to 100 mass % relative to the total amount of the working fluid andhas a temperature glide of 10° C. or less when operating the standardrefrigeration cycle system under the temperature condition (T).

The second working fluid contains, as described above, HFO-1123, R32,and at least one selected from R152a, R161, propane, propylene, carbondioxide, 1234yf, and 1234ze(E) at the content ratios satisfyingExpression A2 and Expression B to Expression E so that the total contentof them becomes 90 to 100 mass % relative to the total amount of theworking fluid and has a temperature glide of 10° C. or less whenoperating the standard refrigeration cycle system under the temperaturecondition (T).

The contents of the respective components in the first working fluid andthe second working fluid are not limited in particular providing thatthe above-described conditions are satisfied. The content of HFO-1123 ineach of the first working fluid and the second working fluid ispreferably 1 mass % or more and 80 mass % or less and more preferably 1mass % or more and 24 mass % or less relative to the total content ofHFO-1123, R32, R152a, R161, propane, propylene, carbon dioxide, 1234yf,and 1234ze(E) from the viewpoint of safety.

In the first working fluid of the present invention, Expression A toExpression E are satisfied, and thereby vaporized and liquefiedcomponents (to be referred to as “other components” simply hereinafter)other than the above-described components may be used together withthese components as necessary providing that the working fluid (R1)having the above-described properties of (A) to (E) is contained by 90to 100 mass % relative to the total amount of the working fluid and theabove-described property relating to the temperature glide is satisfied.However, it is preferred that containing other components should notimpair the above-described properties of (A) to (E) that the workingfluid (R1) has.

In the second working fluid of the present invention, Expression A2 andExpression B to Expression E are satisfied, and thereby vaporized andliquefied components other than the above-described components may beused together with these components as necessary providing that theworking fluid (R2) having the above-described properties of (A2) and (B)to (E) is contained by 90 to 100 mass % relative to the total amount ofthe working fluid and the above-described property relating to thetemperature glide is satisfied. However, it is preferred that containingother components should not impair the above-described properties of(A2) and (B) to (E) that the working fluid (R2) has.

That is, of the present invention, the first working fluid is preferredto have the above-described properties of (A) to (E) that the workingfluid (R1) has and the second working fluid is preferred to have theabove-described properties of (A2) and (B) to (E) that the working fluid(R2) has. These working fluids of the present invention are particularlypreferred to further have the properties relating to the combustionspeed, RDP_(R410A), RQ_(R410A), and the GWP that are defined aspreferable or more preferable in the working fluid (R1) and the workingfluid (R2) described above. The temperature glide and RCOP_(R410A) ofthe working fluids of the present invention are as described above.

When of the present invention, the first working fluid contains, otherthan the working fluid (R1), other components or the second workingfluid contains, other than the working fluid (R2), other components, thetotal content of the other components in the working fluid is 10 mass %or less relative to 100 mass % of the working fluid, more preferably 8mass % or less, and further preferably 5 mass % or less, and it is mostpreferred that other components should not be contained.

As the other components, there can be cited HFC, HFO, a hydrocarbon,chlorofluoroolefin (CFO), hydrochlouofluoroolefin (HCFO) and so on. Asthe other components, components having less effect on the ozone layerand less effect on global warming are preferred.

Examples of HFC include 1,2-difluoroethane, trifluoroethane,tetrafluoroethane, pentafluoroethane, pentafluoropropane,hexafluoropropane, heptafluoropropane, pentafluorobutane,heptafluorocyclopentane, and so on. As HFC, one may be usedindependently, or two or more may be used in combination.

Examples of HFO include 1,2-difluoroethylene (HFO-1132), 2-fluoropropene(HFO-1261yf), 1,1,2-trifluoropropene (HFO-1243yc),trans-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E)),cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), 3,33-trifluoropropene(HFO-1243zf), (Z)-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), and so on.As HFO, one may be used independently, or two or more may be used incombination.

Examples of a hydrocarbon include cyclopropane, butane, isobutane,pentane, isopentane and so on. As the hydrocarbon, one may be usedindependently, or two or more may be used in combination.

Examples of CFO include chlorofluoropropene, chlorofluoroethylene and soon. From the viewpoint of easily suppressing the flammability of theworking fluid without greatly reducing the cycle performance of theworking fluid, 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya),1,3-dichloro-1,2,3,3-tetrafluoropropene (CFO-1214yb),1,2-dichloro-1,2-difluoroethylene (CFO-1112) are preferred as CFO. AsCFO, one may be used independently, or two or more may be used incombination.

Examples of HCFO include hydrochlorofluoropropene,hydrochlorofluoroethylene and so on. From the viewpoint of easilysuppressing the flammability of the working fluid without greatlyreducing the cycle performance of the working fluid,1-chloro-2,3,3,3,3-tetrafluoropropene (HCFO-1224yd),1-chloro-1,2-difluoroethylene (HCFO-1122) are preferred as HCFO. AsHCFO, one may be used independently, or two or more may be used incombination.

<Composition for Heat Cycle System>

The working fluid of the present invention is normally mixed with alubricating oil when applied to a heat cycle system and the mixture canbe used as a composition for heat cycle system. The composition for heatcycle system containing the working fluid of the present invention andthe lubricating oil may further contain, besides these, known additivessuch as a stabilizer and a leakage detection substance.

(Lubricating Oil)

In the heat cycle system, the aforementioned working fluid may be usedas a mixture with the lubricating oil. As the lubricating oil, a knownlubricating oil used in heat cycle systems can be employed. Thelubricating oil is contained together with the above-described workingfluid in the composition for heat cycle system, circulates in the heatcycle system, and functions as a lubricating oil in particularly acompressor in the heat cycle system. In the heat cycle system, thelubricating oil is preferably one that ensures a lubricating ability andthe hermeticity of the compressor and at the same time has sufficientcompatibility with the working fluid under low-temperature conditions.From this point of view, the dynamic viscosity of the lubricating oil at40° C. is preferably 1 to 750 mm²/sec and more preferably 1 to 400mm²/sec. Further, its dynamic viscosity at 100° C. is preferably 1 to100 mm²/sec, and more preferably 1 to 50 mm²/sec.

Examples of the lubricating oil include an ester-based lubricating oil,an ether-based lubricating oil, a fluorine-based lubricating oil, ahydrocarbon-based synthetic oil, a mineral oil, and so on.

The ester-based lubricating oil is an oily ester compound that has anester bond in its molecule, and preferably has the above-describeddynamic viscosity. Examples of the ester-based lubricating oil includedibasic acid ester, polyol ester, complex ester, polyol carbonate ester,and so on.

The dibasic acid ester is preferably an ester of dibasic acid with acarbon number of 5 to 10 (glutaric acid, adipic acid, pimelic acid,suberic acid, azelaic acid, sebacic acid, or the like) and monohydricalcohol with a carbon number of 1 to 15 that has a straight-chain alkylgroup or a branched alkyl group (methanol, ethanol, propanol, butanol,pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol,dodecanol, tridecanol, tetradecanol, pentadecanol, 2-ethylhexanol,isodecyl alcohol, 3-ethyl-3-hexanol, or the like). Concrete examplesthereof include ditridecyl glutarate, di(2-ethylhexyl)adipate,diisodecyl adipate, ditridecyl adipate, di(3-ethyl-3-hexyl)sebacate, andso on.

The polyol ester is an ester synthesized from polyhydric alcohol andfatty acid (carboxylic acid).

The polyol ester is preferably an ester of diol (ethylene glycol,1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol,1,5-pentanediol, neopentyl glycol, 1,7-heptanediol, 1,12-dodecanediol,or the like) or polyol having 3 to 20 hydroxyl groups(trimethylolethane, trimethylolpropane, trimethylolbutane,pentaerythritol, glycerin, sorbitol, sorbitan, sorbitol glycerincondensate, or the like) and fatty acid with a carbon number of 6 to 20(straight-chain or branched fatty acid such as hexanoic acid, heptanoicacid, octanoic acid, 2-ethylhexanoic acid, pelargonic acid, decanoicacid, undecanoic acid, dodecanoic acid, eicosanoic acid, or oleic acid,fatty acid having quaternary c carbon atoms, or the like). The polyolester may have a free hydroxyl group.

The polyol ester is more preferably an ester (trimethylolpropanetripelargonate, pentaerythritol 2-ethylhexanoate, pentaerythritoltetrapelargonate, or the like) of hindered alcohol (neopentyl glycol,trimethylolethane, trimethylolpropane, trimethylolbutane,pentaerythritol or the like).

The complex ester is a combination (complex) of a plurality of types ofesters. The complex ester oil is an oligoester of at least one selectedfrom fatty acid and dibasic acid, and polyol. Examples of the fattyacid, the dibasic acid, and the polyol include the same ones as thosecited as the dibasic acid ester and the polyol ester.

The polyol carbonate ester is an ester of carbonic acid and polyol, or aring-opening polymer of a cyclic alkylene carbonate. Examples of thepolyol include the same diols, polyols, and so on as those cited as theabove-described polyol ester.

The ether-based lubricating oil is an oily ether compound that has anether bond in its molecule, and preferably, has the above-describeddynamic viscosity. Examples of the ether-based lubricating oil includepolyalkylene glycol, polyvinyl ether, and so on.

The polyalkylene glycol is a compound having a plurality of oxyalkyleneunits, in other words, is a polymer or a copolymer of alkylene oxide.

Examples of the polyalkylene glycol include polyalkylene polyolsobtained by a method of polymerizing alkylene oxide with a carbon numberof 2 to 4 (ethylene oxide, propylene oxide, or the like), using water,alkane monool, the aforementioned diol, the aforementioned polyol, orthe like as an initiator, those in which some or all of hydroxyl groupsof the above are turned into alkyl ether, and so on.

The number of types of the oxyalkylene units in one molecule of thepolyalkylene glycol may be one or may be two or more. The polyalkyleneglycol is preferably one including at least an oxypropylene unit in onemolecule, and is more preferably polypropylene glycol or a dialkyl etherof polypropylene glycol.

The polyvinyl ether is a polymer having at least a polymer unit derivedfrom a vinyl ether monomer.

Examples of the polyvinyl ether include a polymer of vinyl ethermonomers, a copolymer of a vinyl ether monomer and a hydrocarbon monomerhaving an olefinic double bond, a copolymer of a vinyl ether monomer anda vinyl ether monomer having a plurality of oxyalkylene units, and soon. Alkylene oxide forming the oxyalkylene unit is preferably any ofthose cited as the polyalkylene glycol as an example. These polymerseach may be a block or random copolymer.

The vinyl ether monomer is preferably alkyl vinyl ether, and its alkylgroup is preferably an alkyl group with a carbon number of 6 or less.Further, as the vinyl ether monomer, one may be used independently, ortwo or more may be used in combination. Examples of the hydrocarbonmonomer having the olefinic double bond include ethylene, propylene,various types of butenes, various types of pentenes, various types ofhexenes, various types of heptenes, various types of octenes,diisobutylene, triisobutylene, styrene, α-methylstyrene, various typesof alkyl-substituted styrenes, and so on. As the hydrocarbon monomerhaving the olefinic double bond, one may be used independently, or twoor more may be used in combination.

The fluorine-based lubricating oil is an oily fluorine-containingcompound that has a fluorine atom in its molecule and, preferably, hasthe above-described dynamic viscosity.

Examples of the fluorine-based lubricating oil include a compound inwhich a hydrogen atom of a later-described mineral oil orhydrocarbon-based synthetic oil (for example, poly α-olefin, alkylbenzene, alkyl naphthalene, or the like) is replaced by a fluorine atom,a perfluoropolyether oil, a fluorinated silicone oil, and so on.

The mineral oil is obtained by refining a lubricating oil fractionobtained through atmospheric distillation or reduced-pressuredistillation of a crude oil, by an appropriate combination of refiningtreatments (solvent deasphalting, solvent extraction, hydrocracking,solvent dewaxing, contact dewaxing, hydrorefining, clay treatment, andso on). Examples of the mineral oil include a paraffinic mineral oil, anaphthenic mineral oil, and so on.

The hydrocarbon-based synthetic oil is an oily synthesized compoundwhose molecule is composed only of a carbon atom and a hydrogen atom andthat preferably, has the above-described dynamic viscosity. Examples ofthe hydrocarbon-based synthetic oil include poly α-olefin, alkylbenzene, alkyl naphthalene, and so on.

As the lubricating oil, one may be used independently, or two or moremay be used in combination. As the lubricating oil, one or both ofpolyol ester and polyalkylene glycol are preferred from the viewpoint ofcompatibility with the working fluid, and the polyalkylene glycol isparticularly preferred from the viewpoint of obtaining a prominentoxidation prevention effect by a stabilizer.

In the case where the mixture of the working fluid and the lubricatingoil is used, the used amount of the lubricating oil may be any, providedthat it falls within a range not causing a great reduction in the effectof the present invention, and may be appropriately determined accordingto its use, a type of the compressor, and so on. The total mass ratio ofthe lubricating oil in the composition for heat cycle system to thetotal mass, that is, 100 parts by mass, of the working fluid ispreferably 10 to 100 parts by mass, and more preferably 20 to 50 partsby mass.

(Stabilizer)

The stabilizer is a component that improves the stability of the workingfluid against heat and oxidation. Examples of the stabilizer include anoxidation resistance improver, a heat resistance improver, a metaldeactivator, and so on.

The oxidation resistance improver is a stabilizer that stabilizes theworking fluid by suppressing decomposition of the working fluid mainlydue to oxygen, under a condition that the working fluid is repeatedlycompressed heated in the heat cycle system.

Examples of the oxidation resistance improver includeN,N′-diphenylphenylenediamine, p-octyldiphenylamine,p,p′-dioctyldiphenylamine, N-phenyl-1-naphthylamine,N-phenyl-2-naphthylamine, N-(p-dodecyl)phenyl-2-naphthylamine,di-1-naphthylamine, di-2-naphthylamine, N-alkylphenothiazine,6-(t-butyl)phenol, 2,6-di-(t-butyl)phenol,4-methyl-2,6-di-(t-butyl)phenol,4,4′-methylenebis(2,6-di-t-butylphenol), and so on. As the oxidationresistance improver, one may be used independently, or two or more maybe used in combination.

The heat resistance improver is a stabilizer that stabilizes the workingfluid by suppressing decomposition of the working fluid mainly due toheat, under a condition that the working fluid is repeatedlycompressed-heated in the heat cycle system. Examples of the heatresistance improver include the same ones as those cited as the examplesof the oxidation resistance improver. As the heat resistance improver,one may be used independently, or two or more may be used incombination.

The metal deactivator is used for the purpose of preventing a metalmaterial in the heat cycle system from adversely affecting the workingfluid and the lubricating oil or protecting the metal material from theworking fluid and the lubricating oil. Concrete examples thereof includea chemical agent that forms a coating film on a surface of the metalmaterial, and so on.

Examples of the metal deactivator include imidazole, benzimidazole,2-mercaptobenzothiazole, 2,5-dimercaptothiadiazole,salicylidine-propylenediamine, pyrazole, benzotriazole, tolyltriazole,2-methylbenzimidazole, 3,5-dimethylpyrazole, methylenebis-benzotriazole,organic acid, or esters of these, primary, secondary, or tertiaryaliphatic amine, amine salt of organic acid or inorganic acid, aheterocyclic nitrogen-containing compound, amine salt of alkyl acidphosphate, or derivatives of these, and so on.

The total mass ratio of the stabilizer to the total mass (100 mass %) ofthe working fluid in the composition for heat cycle system may be any,provided that it falls within a range not causing a great reduction inthe effect of the present invention, and is preferably 5 mass % or less,and more preferably 1 mass % or less.

(Known Additives Such as the Leakage Detection Substance)

The leakage detection substance refers to a substance in general that isadded for the purpose of facilitating the detection of the working fluidand so on, using smell, fluorescence, or the like when the working fluidand so on leak from the heat cycle system.

Examples of the leakage detection substance include an ultravioletfluorescent dye, an odor gas, an odor masking agent, and so on. Examplesof the ultraviolet fluorescent dye include known ultraviolet fluorescentdyes such as those described in the specification of U.S. Pat. No.4,249,412, JP-A-H10-502737, JP-A-2007-511645, JP-A-2008-500437, andJP-A-2008-531836.

The odor masking agent refers to a substance in general such as acompound or a perfume that is added in the case of the working fluid,the lubricating oil, and a later-described solubilizing agent having anunpleasant odor, for the purpose of improving the odor while maintainingproperties of themselves. Examples of the odor masking agent includeknown perfumes such as those described in JP-A-2008-500437 andJP-A-2008-531836.

In the case of using the leakage detection substance, the solubilizingagent that improves solubility of the leakage detection substance in theworking fluid may be used. Examples of the solubilizing agent includethose described in JP-A-2007-511645, JP-A-2008-500437, andJP-A-2008-531836, and so on.

The total mass ratio of the leakage detection substance to the totalmass (100 mass %) of the working fluid in the composition for heat cyclesystem may be any, provided that it falls within a range not causing agreat reduction in the effect of the present invention, and ispreferably 2 mass % or less, and more preferably 0.5 mass % or less.

<Heat Cycle System>

The heat cycle system of the present invention is a system using thecomposition for heat cycle system of the present invention. The heatcycle system of the present invention may be a heat pump systemutilizing hot heat obtained in a condenser or may be a refrigerationcycle system utilizing cold heat obtained in an evaporator.

Concrete examples of the heat cycle system of the present inventioninclude a refrigerating apparatus, an air-conditioning apparatus, apower generation system, a heat transport apparatus, a secondary coolingmachine, and so on. Among them, the heat cycle system of the presentinvention is preferably used as an air-conditioning apparatus that isoften installed outdoors or the like because this heat cycle system canexhibit cycle performance stably and safely even in a high-temperatureworking environment. Further, the heat cycle system of the presentinvention is also preferably used as a refrigerating apparatus.

Concrete examples of the air-conditioning apparatus include a roomair-conditioner, packaged air-conditioners (such as a store packagedair-conditioner, a building packaged air-conditioner, and a plantpackaged air-conditioner), a gas engine heat pump, a trainair-conditioning system, an automobile air-conditioning system, and soon.

Concrete examples of the refrigerating apparatus include showcases (suchas a built-in showcase and a separate showcase), an industrialfridge-freezer, a vending machine, an ice making machine, and so on.

As the power generation system, a power generation system by Rankinecycle system is preferred. As the power generation system, concretely,there can be cited as an example a system in which in an evaporator, aworking fluid is heated by geothermal energy, solar heat, waste heat ina medium-to-high temperature range at about 50 to 200° C., or the like,the vaporized working fluid in a high temperature and high pressurestate is adiabatically expanded by an expansion device, and a powergenerator is driven by the work generated by the adiabatic expansion tothereby perform power generation.

Further, the heat cycle system of the present invention may be a heattransport apparatus. As the heat transport apparatus, a latent heattransport apparatus is preferred.

As the latent heat transport apparatus, there can be cited a heat pipeconducting latent heat transport utilizing a phenomenon such asevaporation, boiling, or condensation of a working fluid filled in anapparatus and a two-phase closed thermosiphon apparatus. The heat pipeis applied to a relatively small-sized cooling apparatus such as acooling apparatus of a heat generation part of a semiconductor elementand electronic equipment. The two-phase closed thermosiphon apparatus iswidely utilized for a gas/gas heat exchanger, accelerating snow meltingand preventing freezing of roads, and the like because it does notrequire a wig and its structure is simple.

Incidentally, at the time of operation of the heat cycle system, inorder to prevent occurrence of failure due to mixture of moisture andmixture of noncondensing gas such as oxygen, it is preferred to providea means for suppressing the mixture of these.

Moisture, if mixed into the heat cycle system, may cause problems whenthe heat cycle system is used particularly at low temperature. Forexample, problems such as freezing in a capillary tube, hydrolysis ofthe working fluid and the lubricating oil, deterioration of material dueto acid components generated in the cycle, generation of contaminantsand so on occur. In particular, when the lubricating oil is thepolyglycol oil, the polyolester oil or the like, the lubricating oil isextremely high in hygroscopicity, is likely to cause a hydrolysisreaction, and decreases in characteristics as the lubricating oil,resulting in a major cause to lose the long-term reliabliability of thecompressor. Accordingly, to suppress the hydrolysis of the lubricatingoil, it is necessary to control the moisture concentration in the heatcycle system.

Examples of a method of controlling the moisture concentration in theheat cycle system include a method of using a moisture removing meanssuch as a drying agent (silica gel, activated alumina, zeolite, or thelike), or the like. Bringing the drying agent into contact with a liquidcomposition for heat cycle system is preferred in terms of dehydrationefficiency. For example, the drying agent is preferably placed at anoutlet of the condenser 12 or an inlet of the evaporator 14 to bring thedrying agent into contact with the composition for heat cycle system.

As the drying agent, a zeolite-based drying agent is preferred from theviewpoint of chemical reactivity between the drying agent and thecomposition for heat cycle system and hygroscopic capacity of the dryingagent.

As the zeolite-based drying agent, a zeolite-based drying agentcontaining a compound expressed by Formula (3) below as a main componentis preferred from the viewpoint of being excellent in hygroscopiccapacity in the case of using a lubricating oil higher in moistureabsorption amount than a conventional mineral lubricating oil.

M_(2/n)O.Al₂O₃ .xSiO₂ .yH₂O  (3)

Where M is an element of Group 1 such as Na or K or an element of Group2 such as Ca, n is a valence of M, and x, y are values determined by acrystal structure. By changing M, a pore diameter can be adjusted.

In selecting the drying agent, a pore diameter and a breaking strengthare important. In the case of using a drying agent having a porediameter larger than a molecular diameter of the working fluid containedin the composition for heat cycle system, the working fluid is absorbedinto the drying agent, and as a result, a chemical reaction occursbetween the working fluid and the drying agent, thereby causingunfavorable phenomena such as generation of noncondensing gas, adecrease in strength of the drying agent, and a decrease in absorptioncapacity.

Accordingly, as the drying agent, it is preferred to use a zeolite-baseddrying agent having a small pore diameter. In particular, asodium-potassium A type synthetic zeolite having a pore diameter of 3.5angstrom or less is preferred. Applying the sodium-potassium A typesynthetic zeolite having a pore diameter smaller than the moleculardiameter of the working fluid makes it possible to selectively absorband remove only moisture in the heat cycle system without absorbing theworking fluid. In other words, since the absorption of the working fluidto the drying agent is unlikely to occur, thermal decomposition becomesless likely to occur, thereby making it possible to suppressdeterioration of the material forming the heat cycle system andoccurrence of contaminants.

The size of the zeolite-based drying agent is preferably about 0.5 to 5mm as a representative value of the particle size since thezeolite-based drying agent having a too-small size causes clogging ofthe valve or pipe small portions in the heat cycle system, whereas thezeolite-based drying agent having a too-large size decreases the dryingability. The shape of the zeolite-based drying agent is preferablygranular or cylindrical.

The zeolite-based drying agent can be made into an arbitrary shape bysolidifying powdery zeolite with a binder (bentonite or the like). Aslong as the zeolite-based drying agent is used as a main body, anotherdrying agent (silica gel, activated alumina or the like) may be usedtogether. The use ratio of the zeolite-based drying agent to thecomposition for heat cycle system is not particularly limited.

Further, the noncondensing gas, if entering the inside of the heat cyclesystem, has adverse effects such as failure of heat transfer in thecondenser and the evaporator and an increase in working pressure, andtherefore the mixture of the noncondensing gas needs to be suppressed asmuch as possible. In particular, oxygen being one noncondensing gasreacts with the working fluid and the lubricating oil to promotedecomposition.

The concentration of the noncondensing gas is preferably 1.5 volume % orless and particularly preferably 0.5 volume % or less by volume percentwith respect to the working fluid in a gas phase part of the workingfluid.

According to the above-described heat cycle system of the presentinvention, use of the working fluid of the present invention makes itpossible to obtain practically sufficient cycle performance high insafety while suppressing the effect on global warming.

EXAMPLES

Hereinafter, the present invention will be explained in detail byexamples, but the present invention is not limited to the followingexamples. Examples 1 to 7, 14 to 16, 22 to 24, 29 to 31, 36 to 40, 45 to51, 56 to 58, 62 to 64, 69 to 71, 75 to 77, 80, 81, 85, 86, 91 to 96,and 98 to 101 are examples, and Examples 8 to 13, 17 to 21, 25 to 28, 32to 35, 41 to 44, 52 to 55, 59 to 61, 65 to 68, 72 to 74, 78, 79, 82 to84, 87 to 90, and 97 are comparative examples.

Examples 1 to 101

In Examples 1 to 101, working fluids obtained by mixing HFO-1123, R32,and one or more selected from R152a, R161, propane, propylene, carbondioxide, 1234yf, and 1234ze(E) at ratios illustrated in Table 2 to Table6 were fabricated, and of the working fluids, a GWP, self-decomposition,a combustion speed, RDP_(R410)A, RQ_(R410A), RCOP_(R410A), and atemperature glide were calculated or measured by the above-describedmethods. Results are illustrated in Table 2 to Table 6 together withcompositions.

TABLE 2 Self Combustion Compound/ Composition decomposition speedExample Evaluation item [Unit] (Mass %) GWP (215° C., 10MPaG) [cm/sec] 1HFO-1123/R32/Carbon dioxide/R161 61/22/10/7 149.6 Absent 7.8 2HFO-1123/R32/Carbon dioxide/R161 56/22/18/4 149.3 Absent 5.6 3HFO-1123/R32/Carbon dioxide/R161 50/22/20/8 149.8 Absent 8.0 4HFO-1123/R32/Carbon dioxide/R161 63/22/15/0 148.8 Absent <4 5HFO-1123/R32/Carbon dioxide/R161 60/22/18/0 148.9 Absent <4 6HFO-1123/R32/Carbon dioxide/R161 48/22/22/8 149.8 Absent 7.9 7HFO-1123/R32/Carbon dioxide/R161 55/22/19/4 149.3 Absent 5.6 8HFO-1123/R32/Carbon dioxide/R161 53/22/25/0 148.9 Absent <4 9HFO-1123/R32/Carbon dioxide/R161 42/22/31/5 149.5 Absent 5.7 10HFO-1123/R32/Carbon dioxide/R161 68/22/10/0 148.8 Present <4 11HFO-1123/R32/Carbon dioxide/R161 66/22/5/7 149.6 Present 8.0 12HFO-1123/R32/Carbon dioxide/R161 60/22/6/12 150.2 Absent >10 13HFO-1123/R32/Carbon dioxide/R161 48/22/17/13 150.4 Absent >10 14HFO-1123/R32/Carbon dioxide/R161 64/15/18/3 102.0 Absent 4.8 15HFO-1123/R32/Carbon dioxide/R161 54/15/22/9 102.7 Absent 8.3 16HFO-1123/R32/Carbon dioxide/R161 62/15/14/9 102.7 Absent 8.7 17HFO-1123/R32/Carbon dioxide/R161 48/15/30/7 102.5 Absent 6.8 18HFO-1123/R32/Carbon dioxide/R161 52/15/21/12 103.1 Absent >10 19HFO-1123/R32/Carbon dioxide/R161 61/15/12/12 103.0 Absent >10 20HFO-1123/R32/Carbon dioxide/R161 58/15/27/0 101.7 Absent <4 Achieved (◯)or Not Temperature Achieved(X) glide the Example RCOP_(R410A) RQ_(R410A)[° C.] RDP_(R410A) condition  1 0.98 1.39 4.9 1.42 ◯  2 0.95 1.58. 6.31.65 ◯  3 0.97 1.57 7.5 1.61 ◯  4 0.94 1.56 4.8 1.67 ◯  5 0.93 1.62 5.41.74 ◯  6 0.96 1.60 7.8 1.66 ◯  7 0.95 1.59 6.4 1.68 ◯  8 0.90 1.73 6.21.90 X  9 0.92 1.77 8.1 1.90 X 10 0.95 1.46 3.7 1.54 X 11 0.98 1.27 3.31.30 X 12 1.00 1.25 4.4 1.26 X 13 0.99 1.45 7.6 1.45 X 14 0.93 1.59 6.21.71 ◯ 15 0.95 1.60 8.5 1.67 ◯ 16 0.98 1.45 6.8 1.49 ◯ 17 0.91 1.74 8.81.88 X 18 0.97 1.55 9.0 1.58 X 19 0.99 1.38 6.9 1.40 X 20 0.87 1.76 6.12.01 X

TABLE 3 Self Combustion Compound/ Composition decomposition speedExample Evaluation item [Unit] (Mass %) GWP (215° C., 10MPaG) [cm/sec]21 HFO-1123/R32/Carbon dioxide/R161 70/15/10/5 102.2 Present 6.4 22HFO-1123/R32/Carbon dioxide/R161 67/10/19/4 68.4 Absent 5.3 23HFO-1123/R32/Carbon dioxide/R161 65/10/16/9 68.9 Absent 8.5 24HFO-1123/R32/Carbon dioxide/R161 61/10/22/7 68.7 Absent 7.0 25HFO-1123/R32/Carbon dioxide/R161 55/10/23/12 69.3 Absent >10 26HFO-1123/R32/Carbon dioxide/R161 64/10/26/0 68.0 Absent <4 27HFO-1123/R32/Carbon dioxide/R161 52/10/31/7 68.8 Absent 6.6 28HFO-1123/R32/Carbon dioxide/R161 74/10/11/5 68.4 Present 6.2 29HFO-1123/R32/Carbon dioxide/R161 69/5/20/6 34.9 Absent 6.4 30HFO-1123/R32/Carbon dioxide/R161 68/5/18/9 35.2 Absent 8.3 31HFO-1123/R32/Carbon dioxide/R161 63/5/23/9 35.2 Absent 8.1 32HFO-1123/R32/Carbon dioxide/R161 70/5/23/2 34.4 Absent <4 33HFO-1123/R32/Carbon dioxide/R161 67/5/16/12 35.6 Absent >10 34HFO-1123/R32/Carbon dioxide/R161 60/5/28/7 35.1 Absent 6.6 35HFO-1123/R32/Carbon dioxide/R161 76/5/13/6 34.8 Present 6.7 36HFO-1123/R32/1234yf/R161 48/22/30/0 149.8 Absent <4 37HFO-1123/R32/1234yf/R161 49/22/24/5 150.2 Absent 6.7 38HFO-1123/R32/1234yf/R161 45/22/33/0 150.0 Absent <4 39HFO-1123/R32/1234yf/R161 50/22/19/9 150.5 Absent 9.2 40HFO-1123/R32/1234yf/R161 44/22/26/8 150.6 Absent 7.7 Achieved (◯)Temperature or Not glide Achieved(X) Example RCOP_(R410A) RQ_(R410A) [°C.] RDP_(R410A) the condition 21 0.97 1.41 4.9 1.47 X 22 0.93 1.60 6.91.74 ◯ 23 0.97 1.49 7.7 1.55 ◯ 24 0.94 1.62 8.3 1.73 ◯ 25 0.96 1.58 9.91.64 X 26 0.86 1.74 6.0 2.03 X 27 0.90 1.75 9.1 1.94 X 28 0.96 1.43 5.41.51 X 29 0.93 1.59 8.1 1.73 ◯ 30 0.96 1.53 8.7 1.61 ◯ 31 0.94 1.61 9.51.73 ◯ 32 0.88 1.67 6.9 1.92 X 33 0.98 1.46 9.0 1.50 X 34 0.90 1.71 9.31.90 X 35 0.96 1.46 6.6 1.55 X 36 1.01 0.95 6.4 0.95 ◯ 37 1.01 0.96 5.60.97 ◯ 38 1.02 0.92 6.6 0.93 ◯ 39 1.01 0.97 5.0 0.98 ◯ 40 1.02 0.93 5.70.92 ◯

TABLE 4 Self Combustion Compound/ Composition decomposition speedExample Evaluation item [Unit] (Mass %) GWP (215° C., 10MPaG) [cm/sec]41 HFO-1123/R32/1234yf/R161 59/22/14/5 149.8 Present 6.8 42HFO-1123/R32/1234yf/R161 50/22/16/12 150.7 Absent >10 43HFO-1123/R32/1234yf/R161 42/22/24/12 151.0 Absent >10 44HFO-1123/R32/1234yf/R161 40/22/33/5 150.5 Absent 6.6 45HFO-1123/R32/1234ze(E)/R161 48/22/29/1 150.5 Absent <4 46HFO-1123/R32/1234ze(E)/R161 49/22/25/4 150.6 Absent 5.4 47HFO-1123/R32/1234ze(E)/R161 50/22/20/8 150.8 Absent 8.0 48HFO-1123/R32/1234ze(E)/R161 45/22/26/7 151.0 Absent 5.2 49HFO-1123/R32/1234ze(E)/R161 45/22/29/4 150.9 Absent 5.2 50HFO-1123/R32/1234ze(E)/R161 51/22/18/9 150.8 Absent 8.8 51HFO-1123/R32/1234ze(E)/R161 48/22/30/0 150.4 Absent <4 52HFO-1123/R32/1234ze(E)/R161 51/22/15/12 151.0 Absent >10 53HFO-1123/R32/1234ze(E)/R161 42/22/31/5 151.1 Absent 5.7 54HFO-1123/R32/1234ze(E)/R161 59/22/14/5 150.1 Present 6.4 55HFO-1123/R32/1234ze(E)/R161 45/22/21/12 151.3 Absent >10 56HFO-1123/R32/Carbon dioxide/Propane 64/22/10/4 148.9 Absent 7.9 57HFO-1123/R32/Carbon dioxide/Propane 64/22/13/1 148.9 Absent 4.5 58HFO-1123/R32/Carbon dioxide/Propane 55/22/19/4 149.0 Absent 6.9 59HFO-1123/R32/Carbon dioxide/Propane 54/22/17/7 149.1 Absent >10 60HFO-1123/R32/Carbon dioxide/Propane 65/22/5/8 149.0 Absent >10 Achieved(◯) or Not Temperature Achieved(X) glide the Example RCOP_(R410A)RQ_(R410A) [° C.] RDP_(R410A) condition 41 0.99 1.03 4.2 1.06 X 42 1.010.98 4.7 0.98 X 43 1.03 0.92 5.5 0.91 X 44 1.03 0.90 6.3 0.89 X 45 1.000.94 8.0 0.95 ◯ 46 1.00 0.95 7.2 0.96 ◯ 47 1.00 0.96 6.3 0.97 ◯ 48 1.010.93 7.4 0.93 ◯ 49 1.01 0.92 7.9 0.92 ◯ 50 1.00 0.97 5.9 0.98 ◯ 51 1.010.94 8.2 0.95 ◯ 52 1.00 0.98 5.4 0.98 X 53 1.02 0.90 8.2 0.90 X 54 0.991.03 4.8 1.06 X 55 1.02 0.93 6.5 0.93 X 56 0.96 1.43 3.9 1.50 ◯ 57 0.951.51 4.4 1.61 ◯ 58 0.93 1.60 5.8 1.72 ◯ 59 0.95 1.55 5.9 1.64 X 60 0.971.27 2.8 1.32 X

TABLE 5 Self Combustion Compound/ Composition decomposition speedExample Evaluation item [Unit] (Mass %) GWP (215° C., 10MPaG) [cm/sec]61 HFO-1123/R32/Carbon dioxide/Propane 70/22/5/3 148.9 Present 7.2 62HFO-1123/R32/1234yf/Propane 56/22/17/5 149.5 Absent 9.7 63HFO-1123/R32/1234yf/Propane 44/22/30/4 150.0 Absent 9.7 64HFO-1123/R32/1234yf/Propane 51/22/25/2 149.7 Absent 5.9 65HFO-1123/R32/1234yf/Propane 60/22/10/8 149.3 Absent >10 66HFO-1123/R32/1234yf/Propane 41/22/35/2 150.1 Absent 5.8 67HFO-1123/R32/1234yf/Propane 44/22/27/7 149.9 Absent >10 68HFO-1123/R32/1234yf/Propane 62/22/14/2 149.3 Present 6.1 69HFO-1123/R32/1234ze(E)/Propane 51/22/25/2 150.2 Absent 5.2 70HFO-1123/R32/1234ze(E)/Propane 45/22/29/4 150.5 Absent 6.2 71HFO-1123/R32/1234ze(E)/Propane 46/22/26/6 150.4 Absent 9.8 72HFO-1123/R32/1234ze(E)/Propane 60/22/10/8 149.5 Absent >10 73HFO-1123/R32/1234ze(E)/Propane 43/22/33/2 150.7 Absent 4.9 74HFO-1123/R32/1234ze(E)/Propane 63/22/13/2 149.5 Present 5.7 75HFO-1123/R32/Carbon dioxide/Propane 62/22/11/5 148.9 Absent 7.1 76HFO-1123/R32/Carbon dioxide/Propane 63/22/13/2 148.9 Absent 5.2 77HFO-1123/R32/Carbon dioxide/Propane 54/22/20/4 148.9 Absent 4.9 78HFO-1123/R32/Carbon dioxide/Propane 60/22/9/9 148.9 Absent >10 79HFO-1123/R32/Carbon dioxide/Propane 68/22/7/3 148.8 Present 6.4 80HFO-1123/R32/1234yf/Propylene 49/22/25/4 149.7 Absent 6.2 Achieved (◯)or Not Temperature Achieved(X) glide the Example RCOP_(R410A) RQ_(R410A)[° C.] RDP_(R410A) condition 61 0.96 1.31 2.2 1.38 X 62 0.98 1.02 4.01.05 ◯ 63 1.02 0.92 6.1 0.92 ◯ 64 1.00 0.97 5.5 0.99 ◯ 65 0.97 1.05 2.71.10 X 66 1.02 0.90 6.5 0.90 X 67 1.00 0.94 5.2 0.96 X 68 0.97 1.05 3.71.10 X 69 0.99 0.97 6.9 0.99 ◯ 70 1.00 0.93 7.5 0.95 ◯ 71 0.99 0.95 6.60.97 ◯ 72 0.97 1.05 3.0 1.10 X 73 1.01 0.91 8.5 0.92 X 74 0.97 1.06 4.01.11 X 75 0.96 1.45 3.8 1.52 ◯ 76 0.95 1.51 4.3 1.60 ◯ 77 0.93 1.63 5.51.75 ◯ 78 0.96 1.37 3.4 1.44 X 79 0.96 1.37 2.7 1.44 X 80 0.99 0.98 5.41.00 ◯

TABLE 6 Self Combustion Compound/ Composition decomposition speedExample Evaluation item [Unit] (Mass %) GWP (215° C., 10MPaG) [cm/sec]81 HFO-1123/R32/1234yf/Propylene 43/22/31/4 149.9 Absent 6.4 82HFO-1123/R32/1234yf/Propylene 50/22/21/7 149.6 Absent >10 83HFO-1123/R32/1234yf/Propylene 58/22/18/2 149.4 Present 5.5 84HFO-1123/R32/1234yf/Propylene 41/22/35/2 150.1 Absent 5.3 85HFO-1123/R32/1234ze(E)/Propane 50/22/23/5 150.1 Absent 6.8 86HFO-1123/R32/1234ze(E)/Propane 45/22/28/5 150.4 Absent 6.6 87HFO-1123/R32/1234ze(E)/Propane 50/22/20/8 150.0 Absent >10 88HFO-1123/R32/1234ze(E)/Propane 45/22/25/8 150.3 Absent >10 89HFO-1123/R32/1234ze(E)/Propane 42/22/34/2 150.7 Absent 4.4 90HFO-1123/R32/1234ze(E)/Propane 58/22/18/2 149.8 Present 5.0 91HFO-1123/R32/1234ze(E)/Propane 49/22/28/1 150.3 Absent <4 92HFO-1123/R32/Carbon dioxide/R152a 61/22/9/8 158.7 Absent 5.7 93HFO-1123/R32/Carbon dioxide/R152a 55/22/15/8 158.7 Absent 5.4 94HFO-1123/R32/Carbon dioxide/R152a 62/15/3/20 126.3 Absent 8.9 95HFO-1123/R32/Carbon dioxide/R152a 60/18/0/22 149.0 Absent 7.0 96HFO-1123/R32/Carbon dioxide/R152a 61/16/0/23 136.7 Absent 9.9 97HFO-1123/R32/Carbon dioxide/R152a 53/18/0/29 157.6 Absent >10 98HFO-1123-R32/1234yf/R152a 50/22/20/8 159.4 Absent 5.8 99HFO-1123-R32/1234yf/R152a 55/19/6/20 153.5 Absent 9.1 100 HFO-1123/R32/1234ze(E)/R152a 50/22/20/8 159.4 Absent 5.8 101 HFO-1123/R32/1234ze(E)/R152a 55/19/6/20 153.5 Absent 9.1 Achieved (◯) orNot Temperature Achieved(X) glide the Example RCOP_(R410A) RQ_(R410A) [°C.] RDP_(R410A) condition 81 1.01 0.94 6.1 0.95 ◯ 82 0.99 1.00 4.6 1.03X 83 0.98 1.03 4.5 1.07 X 84 1.02 0.91 6.6 0.91 X 85 0.98 0.98 6.2 1.01◯ 86 1.00 0.95 7.4 0.97 ◯ 87 0.98 1.00 5.3 1.04 X 88 0.99 0.97 6.5 0.99X 89 1.01 0.91 8.8 0.91 X 90 0.98 1.02 5.3 1.07 X 91 1.00 0.95 7.7 0.97◯ 92 0.99 1.33 7.6 1.35 ◯ 93 0.98 1.46 9.5 1.49 ◯ 94 1.02 1.06 9.1 1.04◯ 95 1.02 0.95 7.8 0.95 ◯ 96 1.02 0.94 8.0 0.94 ◯ 97 1.04 0.90 9.0 0.87X 98 1.02 0.95 7.0 0.94 ◯ 99 1.02 0.93 8.0 0.92 ◯ 100  1.01 0.94 7.70.94 ◯ 101  1.02 0.93 8.1 0.92 ◯

The working fluid for heat cycle, the composition for heat cycle system,and the heat cycle system using the working fluid and the composition ofthe present invention can be utilized for refrigerating apparatuses(such as a built-in showcase, a separate showcase, an industrialfridge-freezer, a vending machine, and an ice making machine),air-conditioning apparatuses (such as a room air-conditioner, a storepackaged air-conditioner, a building packaged air-conditioner, a plantpackaged air-conditioner, a gas engine heat pump, a trainair-conditioning system, and an automobile air-conditioning system), apower generation system (such as exhaust heat recovery powergeneration), and a heat transport apparatus (such as a heat pipe).

1: A working fluid for heat cycle comprising trifluoroethylene anddifluoromethane, the working fluid for heat cycle further comprising: atleast one compound selected from the group consisting of1,1-difluoroethane, fluoroethane, propane, propylene, carbon dioxide,2,3,3,3-tetrafluoropropene, and (E)-1,3,3,3-tetrafluoropropene, whereinthe total content ratio of trifluoroethylene, difluoromethane,1,1-difluoroethane, fluoroethane, propane, propylene, carbon dioxide,2,3,3,3-tetrafluoropropene, and (E)-1,3,3,3-tetrafluoropropene relativeto the total amount of the working fluid for heat cycle is 90 to 100mass %, content ratios by mass of the respective compounds satisfy allExpressions A, B, C, D and E or all Expressions A2, B, C, D and E belowwhen the total content of trifluoroethylene, difluoromethane,1,1-difluoroethane, fluoroethane, propane, propylene, carbon dioxide,2,3,3,3-tetrafluoropropene, and (E)-1,3,3,3-tetrafluoropropene containedin the working fluid for heat cycle is set to 1, and a temperature glideis 10° C. or less when operating a standard refrigeration cycle systemunder a temperature condition (T) that in the case of the working fluidfor heat cycle being a zeotropic mixture, an average temperature of anevaporation start temperature and an evaporation completion temperatureis 0° C., in the case of the working fluid for heat cycle being anazeotropic mixture, an evaporation temperature is 0° C., in the case ofthe working fluid for heat cycle being a zeotropic mixture, an averagetemperature of a condensation start temperature and a condensationcompletion temperature is 40° C., in the case of the working fluid forheat cycle being an azeotropic mixture, a condensation temperature is40° C., a degree of supercooling (SC) is 5° C., and a degree ofsuperheating (SH) is 5° C.,0<−1.000×[HFO-1123]+1.179×[R32]+1.316×[1234yf]+1.316×[1234ze(E)]+3.831×[CO2]+2.632×[R152a]+2.390×[R161]±6.262×[propane]+2.237×[propylene],  ExpressionA;0<−1.000×[HFO-1123]+1.033×[R32]+0.896×[1234yf]+0.896×[1234ze(E)]+2.891×[CO2]+1.955×[R152a]+1.410×[R161]+3.737×[propane]+1.520×[propylene],  ExpressionA2;10>3.426×[HFO-1123]+5.673×[R32]+2.193×[1234yf]−0.596×[1234ze(E)]−0.768×[CO2]+29.897×[R152a]+64.400×[R161]+118.965×[propane]+94.943×[propylene],  ExpressionB;1.78>1.293×[HFO-1123]+1.029×[R32]+0.369×[1234yf]+0.354×[1234ze(E)]+3.807×[CO2]+0.229×[R152a]+0.406×[R161]+0.568×[propane]+0.719×[propylene],  ExpressionC;0.91<1.214×[HFO-1123]+1.133×[R32]+0.402×[1234yf]+0.346×[1234ze(E)]+3.359×[CO2]+0.323×[R152a]+0.548×[R161]+0.588×[propane]+0.725×[propylene],and  Expression D;160>0.3×[HFO-1123]+675×[R32]+4×[1234yf]+6×[1234ze(E)]+1×[CO2]+124×[R152a]+12×[R161]+3.3×[propane]+1.8×[propylene],  ExpressionE; where in Expression A to Expression E, [HFO-1123] represents thecontent ratio by mass of trifluoroethylene, [R32] represents the contentratio by mass of difluoromethane, [R152a] represents the content ratioby mass of 1,1-difluoroethane, [R161] represents the content ratio bymass of fluoroethane, [propane] represents the content ratio by mass ofpropane, [propylene] represents the content ratio by mass of propylene,[CO2] represents the content ratio by mass of carbon dioxide, [1234yf]represents the content ratio by mass of 2,3,3,3-tetrafluoropropene, and[1234ze(E)] represents the content ratio by mass of(E)-1,3,3,3-tetrafluoropropene respectively when the total content oftrifluoroethylene, difluoromrethane, 1,1-difluoroethane, fluoroethane,propane, propylene, carbon dioxide, 2,3,3,3-tetrafluoropropene, and(E)-1,3,3,3-tetrafluoropropene is set to
 1. 2: The working fluid forheat cycle according to claim 1 satisfying Expression B2 below in placeof Expression B above,8>3.426×[HFO-1123]+5.673×[R32]+2.193×[1234yf]−0.596×[1234ze(E)]−0.768×[CO2]+29.897×[R152a]+64.400×[R161]+118.965×[propane]+94.943×[propylene].  ExpressionB2; 3: The working fluid for heat cycle according to claim 1 satisfyingExpression B3 below in place of Expression B above,6>3.426×[HFO-1123]+5.673×[R32]+2.193×[1234yf]−0.596×[1234ze(E)]−0.768×[CO2]+29.897×[R152a]+64.400×[R161]+118.965×[propane]+94.943×[propylene].  ExpressionB3; 4: The working fluid for heat cycle according to claim 1 satisfyingExpression C3 below in place of Expression C above,1.65>1.293×[HFO-1123]+1.029×[R32]+0.369×[1234yf]+0.354×[1234ze(E)]+3.807×[CO2]+0.229×[R152a]+0.406×[R161]+0.568×[propane]T0.719×[propylene].  Expression C3; 5: The working fluid for heat cycleaccording to claim 1 satisfying Expression D3 below in place ofExpression D above,1<1.214×[HFO-1123]+1.133×[R32]+0.402×[1234yf]+0.346×[1234ze(E)]+3.359×[CO2]+0.323×[R152a]+0.548×[R161]+0.588×[propane]+0.725×[propylene].  ExpressionD3; 6: The working fluid for heat cycle according to claim 1 satisfyingExpression E3 below in place of Expression E above,120>0.3×[HFO-1123]+675×[R32]+4×[1234yf]+6×[1234ze(E)]+1×[CO2]+124×[R152a]+12×[R161]+3.3×[propane]+1.8×[propylene].  ExpressionE3; 7: The working fluid for heat cycle according to claim 1, whereinthe temperature glide is 6° C. or less. 8: The working fluid for heatcycle according to claim 1, wherein a relative coefficient ofperformance (RCOP_(R410A)) calculated by Expression (Y) below is greaterthan 0.9, $\begin{matrix}{{{Relative}\mspace{14mu} {coefficient}\mspace{14mu} {of}\mspace{14mu} {performance}\mspace{14mu} \left( {RCOP}_{R\; 410A} \right)} = \frac{{Coefficient}\mspace{14mu} {of}\mspace{14mu} {performance}\mspace{14mu} {of}\mspace{14mu} {sample}\mspace{14mu} \left( {COP}_{sample} \right)}{{Coefficient}\mspace{14mu} {of}\mspace{14mu} {performance}\mspace{14mu} {of}\mspace{14mu} R\; 410A\mspace{14mu} \left( {COP}_{R\; 410A} \right)}} & (Y)\end{matrix}$ in Expression (Y), R410A represents a mixture ofdifluoromethane and pentafluoroethane at a mass ratio of 1:1 and asample indicates a working fluid to be evaluated relatively, andcoefficients of performance of the sample and R410A each are a valueobtained by dividing an output (kW) when operating the standardrefrigeration cycle system under the temperature condition (T) using thesample and R410A by consumed power (kW) required for the operation. 9:The working fluid for heat cycle according to claim 8, wherein theRCOP_(R410A) is greater than 0.95. 10: The working fluid for heat cycleaccording to claim 1, wherein the content ratio of trifluoroethylenerelative to the total content of trifluoroethylene, difluoromethane,1,1-difluoroethane, fluoroethane, propane, propylene, carbon dioxide,2,3,3,3-tetrafluoropropene, and (E)-1,3,3,3-tetrafluoropropene is 1 mass% or more and 80 mass % or less. 11: The working fluid for heat cycleaccording to claim 1, wherein the content ratio of difluoromethanerelative to the total content of trifluoroethylene, difluoromethane,1,1-difluoroethane, fluoroethane, propane, propylene, carbon dioxide,2,3,3,3-tetrafluoropropene, and (E)-1,3,3,3-tetrafluoropropene is 1 mass% or more and 24 mass % or less. 12: A composition for heat cycle systemcomprising the working fluid for heat cycle according to claim 1 and alubricating oil. 13: A heat cycle system using the composition for heatcycle system according to claim
 12. 14: The heat cycle system accordingto claim 13, wherein the heat cycle system is a refrigerating apparatus,an air-conditioning apparatus, a power generation system, a heattransport apparatus, or a secondary cooling machine.